Integrated methods for chemical synthesis

ABSTRACT

Among other things, the present invention encompasses the applicant&#39;s recognition that epoxide carbonylation can be performed industrially utilizing syngas streams containing hydrogen, carbon monoxide and varying amounts carbon dioxide. Contrary to expectation, the epoxide carbonylation reaction proceeds selectively in the presence of these mixed gas streams and incorporates excess CO in the syngas stream into valuable chemical precursors, resulting in hydrogen streams substantially free of CO. This is economically and environmentally preferable to performing WSGR which releases the excess carbon as CO2. The integrated processes herein therefore provide improved carbon efficiency for processes based on coal or biomass gasification or steam methane reforming.

CROSS REFERENCE TO RELATED APPLICATION(S)

This disclosure is continuation application of application Ser. No.15/314,429, filed on Nov. 28, 2019, published as United StatesApplication Publication 2017/0107103, which is a national stage entry ofPCT/US2015/33232, filed on May 29, 2015, which claims the benefit ofU.S. Provisional Application No. 62/004,978, filed on May 30, 2014, thedisclosure of all is hereby incorporated by reference in its entirety.

BACKGROUND OF THE INVENTION

Interest in finding sustainable methods to produce energy and chemicalscontinues to increase in the face of concerns that anthropogenic carbonemissions may be responsible for global climate change. Among theoptions being considered is the use of biomass to feed chemicalproduction via the output of gasification reactions. This process hasappeal since the processes first developed more than a century ago forcoal gasification can be applied to practically any biomass input, andthe subsequent conversion of the resulting syngas to fuels or chemicalsby well established processes has the potential to provide a diverserange of more sustainable chemical products.

However, a drawback to gasification technology is that it is relativelyinefficient in terms of the percentage of the biomass carbon input tothe gasifier that is actually incorporated into the desired endproducts, typically, less than 50%. This is due in large part to thefact that coal and biomass-derived syngas has a low H₂ to CO ratio(typically around ˜0.7) and must be upgraded by water gas shift reaction(WGSR) prior to utilization in downstream processes such as FischerTropsch (FT) or Methanol-to-olefins (MTO) synthesis that typicallyrequires a H₂:CO ratio around 2. The water gas shift process entails thereaction of a water molecule with a carbon monoxide molecule (from thesyngas), producing CO₂ and hydrogen.CO+H₂O

CO₂+H₂

The resulting CO₂ (22 kg CO₂ per kg of H₂ produced) is emitted to theatmosphere and erodes the carbon efficiency and environmental benefit ofbiomass gasification technologies. Furthermore, the water required forthe WGSR process could otherwise be consumed or used in agriculture, andthe residual water returned from the process is unfit for those useswithout further purification.

A related situation exists for conversion of carbonaceous feedstocks toproduce pure hydrogen streams for use in chemical production (e.g.ammonia production) or for use as a fuel. Here, the preferred process ismethane steam reforming (MSR): CH₄+H₂O

CO+3 H₂. Again, the gas stream produced by MSR is typically treated byWGSR to increase the hydrogen content. However, rather than beingconverted to valuable chemicals, the CO from MSR is instead converted toCO₂ which is then released to the atmosphere.

The present invention provides solutions to these and related problems.

SUMMARY OF THE INVENTION

Among other things, the present invention encompasses the applicant'srecognition that epoxide carbonylation can be performed industriallyutilizing syngas streams containing hydrogen, carbon monoxide andvarying amounts carbon dioxide. Contrary to expectation, the epoxidecarbonylation reaction proceeds selectively in the presence of thesemixed gas streams and incorporates excess CO from the syngas stream intovaluable chemical precursors. Where the goal of biomass gasification isto maximize the amount of biomass-derived carbon converted to valuablechemical products, the present invention has the advantage ofincorporating the CO present in syngas into those products. This iseconomically and environmentally preferable to performing WSGR whichconverts that CO to CO₂, which is then lost to the atmosphere. Theintegrated processes herein therefore provide improved carbon efficiencyfor processes based on coal or biomass gasification or steam methanereforming.

In one aspect, the present invention provides an integrated process forthe conversion of biomass or coal to FT products and commodity chemicalsderived from epoxide carbonylation. In certain embodiments, such methodscomprise the steps of:

-   -   a) in a first reaction zone, contacting syngas derived from        gasification of biomass or coal with an epoxide in the presence        of a carbonylation catalyst thereby consuming carbon monoxide        from the syngas and producing an epoxide carbonylation product,    -   b) recovering an upgraded gas stream from the first reaction        zone wherein the upgraded gas stream has a higher hydrogen to        carbon monoxide ratio than the starting syngas stream,    -   c) in a second reaction zone, utilizing the upgraded gas stream        to conduct a second chemical process requiring a hydrogen to        carbon monoxide ratio higher than the ratio in the industrial        gas stream utilized in step (a).

In certain embodiments of the method above, the second chemical processcomprises the utilization of the syngas with a H₂:CO ratio of ˜2 in aFischer Tropsch synthesis.

In a second aspect, the present invention provides an integrated processfor the production of hydrogen and commodity chemicals derived fromepoxide carbonylation. In certain embodiments, such methods comprise thesteps of:

-   -   a) in a first reaction zone, contacting a syngas stream derived        from biomass or MSW gasification, or a steam reforming process,        with an epoxide in the presence of a carbonylation catalyst        thereby consuming carbon monoxide from the syngas stream and        producing an epoxide carbonylation product,    -   b) recovering an upgraded gas stream from the first reaction        zone wherein the upgraded gas stream has a higher hydrogen to        carbon monoxide ratio than the starting syngas stream, and    -   c) in a second reaction zone, utilizing the upgraded gas stream        to conduct a second chemical process requiring a hydrogen to        carbon monoxide ratio higher than the ratio in the industrial        gas stream utilized in step (a).

In certain embodiments, the epoxide carbonylation product produced instep (a) of the methods above is selected from the group consisting of:optionally substituted beta propiolactone, optionally substitutedsuccinic anhydride, and optionally substituted polypropiolactone. Incertain embodiments, the epoxide in the methods above is ethylene oxideand the epoxide carbonylation product is selected from the groupconsisting of: beta propiolactone, succinic anhydride andpolypropiolactone. In certain embodiments, the epoxide in the methodsabove is propylene oxide and the epoxide carbonylation product isselected from the group consisting of: beta butyrolactone, methylsuccinic anhydride and poly(3-hydroxy butyrate).

In certain embodiments of the methods above, the syngas stream in step(a) is characterized in that it has an H₂ to CO ratio less than 1.2. Incertain embodiments, the upgraded gas stream in step (b) ischaracterized in that it has an H₂ to CO ratio greater than 1.9.

In another aspect, the present invention provides an integrated processfor the production of hydrogen and commodity chemicals derived from betalactone carbonylation. In certain embodiments, such methods comprise thesteps of:

-   -   a) in a first reaction zone, contacting syngas with a beta        propiolactone in the presence of a carbonylation catalyst        thereby consuming carbon monoxide from the syngas and producing        a succinic anhydride product,    -   b) recovering an upgraded gas stream from the first reaction        zone wherein the upgraded gas stream has a higher hydrogen to        carbon monoxide ratio than the starting syngas stream,    -   c) in a second reaction zone, utilizing the upgraded gas stream        to conduct a second chemical process requiring a hydrogen to        carbon monoxide ratio higher than the ratio in the industrial        gas stream utilized in step (a).

In certain embodiments of this aspect, the syngas in step (a) is derivedfrom methane steam reforming (MSR). In certain embodiments, the syngasin step (a) is an upgraded gas stream produced as described in the firsttwo aspects of the methods described above.

In certain embodiments of this aspect, the beta propiolactonecarbonylation reaction zone is operated under conditions such thatsubstantially all of the CO in the syngas stream is consumed.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a schematic of an integrated process according to thepresent invention.

FIG. 2 shows a schematic of an integrated hydrogen production processaccording to the present invention,

FIG. 3 shows a schematic of an alternate process according to thepresent invention,

FIG. 4 shows a schematic of a process according to the present inventionutilizing two carbonylation stages,

FIG. 5 shows a schematic of a process according to the present inventionfor the production of acrylic acid from biomass

FIG. 6 shows a schematic of a process according to the present inventionfor the production of C4 chemicals from biomass

DEFINITIONS

Definitions of specific functional groups and chemical terms aredescribed in more detail below. For purposes of this invention, thechemical elements are identified in accordance with the Periodic Tableof the Elements, CAS version, Handbook of Chemistry and Physics, 75^(th)Ed., inside cover, and specific functional groups are generally definedas described therein. Additionally, general principles of organicchemistry, as well as specific functional moieties and reactivity, aredescribed in Organic Chemistry, Thomas Sorrell, University ScienceBooks, Sausalito, 1999; Smith and March March's Advanced OrganicChemistr. 5^(th) Edition, John Wiley & Sons. Inc., New York, 2001;Larock, Comprehensive Organic Transformations, VCH Publishers, Inc., NewYork, 1989; Carruthers, Some Modern Methods of Organic Synthesis, 3^(rd)Edition, Cambridge University Press, Cambridge, 1987; the entirecontents of each of which are incorporated herein by reference.

Certain compounds of the present invention can comprise one or moreasymmetric centers, and thus can exist in various stereoisomeric forms,e.g., enantiomers and/or diastereomers. Thus, inventive compounds andcompositions thereof may be in the form of an individual enantiomer,diastereomer or geometric isomer, or may be in the form of a mixture ofstereoisomers. In certain embodiments, the compounds of the inventionare enantiopure compounds. In certain other embodiments, mixtures ofenantiomers or diastereomers are provided.

Furthermore, certain compounds, as described herein may have one or moredouble bonds that can exist as either a Z or E isomer, unless otherwiseindicated. The invention additionally encompasses the compounds asindividual isomers substantially free of other isomers andalternatively, as mixtures of various isomers, e.g., racemic mixtures ofenantiomers. In addition to the above-mentioned compounds per se, thisinvention also encompasses compositions comprising one or morecompounds.

As used herein, the term “isomers” includes any and all geometricisomers and stereoisomers. For example “isomers” include cis- andtrans-isomers. E- and Z-isomers, R- and S-enantiomers, diastereomers,(D)-isomers, (L)-isomers, racemic mixtures thereof, and other mixturesthereof, as falling within the scope of the invention. For instance, acompound may, in some embodiments, be provided substantially free of oneor more corresponding stereoisomers, and may also be referred to as“stereochemically enriched.”

Where a particular enantiomer is preferred, it may, in some embodimentsbe provided substantially free of the opposite enantiomer, and may alsobe referred to as “optically enriched.” “Optically enriched,” as usedherein, means that the compound is made up of a significantly greaterproportion of one enantiomer. In certain embodiments the compound ismade up of at least about 90% by weight of an enantiomer. In someembodiments the compound is made up of at least about 95%, 97%, 98%,99%, 99.5%, 99.7%, 99.8%, or 99.9% by weight of an enantiomer. In someembodiments the enantiomeric excess of provided compounds is at leastabout 90%, 95%, 97%, 98%, 99%, 99.5%, 99.7%, 99.8%, or 99.9%. In someembodiments, enantiomers may be isolated from racemic mixtures by anymethod known to those skilled in the art, including chiral high pressureliquid chromatography (HPLC) and the formation and crystallization ofchiral salts or prepared by asymmetric syntheses. See, for example,Jacques, et al., Enantiomers, Racemates and Resolutions (WileyInterscience, New York, 1981); Wilen, S. H., et al., Tetrahedron 33:2725(1977); Eliel. E. L. Stereochemistry of Carbon Compounds (McGraw-Hill, NY, 1962); Wilen. S. H. Tables of Resolving Agents and OpticalResolutions p. 268 (E. L. Eliel, Ed., Univ. of Notre Dame Press, NotreDame, Ind. 1972).

The terms “halo” and “halogen” as used herein refer to an atom selectedfrom fluorine (fluoro, —F), chlorine (chloro, —Cl), bromine (bromo,—Br), and iodine (iodo, —I).

The term “aliphatic” or “aliphatic group”, as used herein, denotes ahydrocarbon moiety that may be straight-chain (i.e., unbranched),branched, or cyclic (including fused, bridging, and spiro-fusedpolycyclic) and may be completely saturated or may contain one or moreunits of unsaturation, but which is not aromatic. Unless otherwisespecified, aliphatic groups contain 1-30 carbon atoms. In certainembodiments, aliphatic groups contain 1-12 carbon atoms. In certainembodiments, aliphatic groups contain 1-8 carbon atoms. In certainembodiments, aliphatic groups contain 1-6 carbon atoms. In someembodiments, aliphatic groups contain 1-5 carbon atoms, in someembodiments, aliphatic groups contain 1-4 carbon atoms, in yet otherembodiments aliphatic groups contain 1-3 carbon atoms, and in yet otherembodiments aliphatic groups contain 1-2 carbon atoms. Suitablealiphatic groups include, but are not limited to, linear or branched,alkyl, alkenyl, and alkynyl groups, and hybrids thereof such as(cycloalkyl)alkyl, (cycloalkenyl)alkyl or (cycloalkyl)alkenyl.

The term “heteroaliphatic,” as used herein, refers to aliphatic groupswherein one or more carbon atoms are independently replaced by one ormore atoms selected from the group consisting of oxygen, sulfur,nitrogen, phosphorus, or boron. In certain embodiments, one or twocarbon atoms are independently replaced by one or more of oxygen,sulfur, nitrogen, or phosphorus. Heteroaliphatic groups may besubstituted or unsubstituted, branched or unbranched, cyclic or acyclic,and include “heterocycle,” “hetercyclyl,” “heterocycloaliphatic,” or“heterocyclic” groups.

The term “epoxide”, as used herein, refers to a substituted orunsubstituted oxirane. Substituted oxiranes include monosubstitutedoxiranes, disubstituted oxiranes, trisubstituted oxiranes, andtetrasubstituted oxiranes. Such epoxides may be further optionallysubstituted as defined herein. In certain embodiments, epoxides comprisea single oxirane moiety. In certain embodiments, epoxides comprise twoor more oxirane moieties.

The term “glycidyl”, as used herein, refers to an oxirane substitutedwith a hydroxyl methyl group or a derivative thereof. The term glycidylas used herein is meant to include moieties having additionalsubstitution on one or more of the carbon atoms of the oxirane ring oron the methylene group of the hydroxymethyl moiety, examples of suchsubstitution may include, but are not limited to: alkyl groups, halogenatoms, aryl groups etc. The terms glycidyl ester, glycidyl acrylate,glydidyl ether etc. denote substitution at the oxygen atom of theabove-mentioned hydroxymethyl group, i.e. that oxygen atom is bonded toan acyl group, an acrylate group, or an alkyl group respectively.

The term “acrylate” or “acrylates” as used herein refer to any acylgroup having a vinyl group adjacent to the acyl carbonyl. The termsencompass mono-, di- and tri-substituted vinyl groups. Examples ofacrylates include, but are not limited to: acrylate, methacrylate,ethacrylate, cinnamate (3-phenylacrylate), crotonate, tiglate, andsenecioate.

The term “polymer”, as used herein, refers to a molecule of highrelative molecular mass, the structure of which comprises the multiplerepetition of units derived, actually or conceptually, from molecules oflow relative molecular mass. In certain embodiments, a polymer iscomprised of only one monomer species (e.g., polyethylene oxide). Incertain embodiments, a polymer of the present invention is a copolymer,terpolymer, heteropolymer, block copolymer, or tapered heteropolymer ofone or more epoxides.

The term “unsaturated”, as used herein, means that a moiety has one ormore double or triple bonds.

The terms “cycloaliphatic”, “carbocycle”, or “carbocyclic”, used aloneor as part of a larger moiety, refer to a saturated or partiallyunsaturated cyclic aliphatic monocyclic, bicyclic, or polycyclic ringsystems, as described herein, having from 3 to 12 members, wherein thealiphatic ring system is optionally substituted as defined above anddescribed herein. Cycloaliphatic groups include, without limitation,cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl,cyclohexenyl, cycloheptyl, cycloheptenyl, cyclooctyl, cyclooctenyl, andcyclooctadienyl. In some embodiments, the cycloalkyl has 3-6 carbons.The terms “cycloaliphatic”, “carbocycle” or “carbocyclic” also includealiphatic rings that are fused to one or more aromatic or nonaromaticrings, such as decahydronaphthyl or tetrahydronaphthyl, where theradical or point of attachment is on the aliphatic ring. In someembodiments, a carbocyclic groups is bicyclic. In some embodiments, acarbocyclic group is tricyclic. In some embodiments, a carbocyclic groupis polycyclic.

The term “alkyl,” as used herein, refers to saturated, straight- orbranched-chain hydrocarbon radicals derived from an aliphatic moietycontaining between one and six carbon atoms by removal of a singlehydrogen atom. Unless otherwise specified, alkyl groups contain 1-12carbon atoms. In certain embodiments, alkyl groups contain 1-8 carbonatoms. In certain embodiments, alkyl groups contain 1-6 carbon atoms. Insome embodiments, alkyl groups contain 1-5 carbon atoms, in someembodiments, alkyl groups contain 1-4 carbon atoms, in yet otherembodiments alkyl groups contain 1-3 carbon atoms, and in yet otherembodiments alkyl groups contain 1-2 carbon atoms. Examples of alkylradicals include, but are not limited to, methyl, ethyl, n-propyl,isopropyl, n-butyl, iso-butyl, sec-butyl, sec-pentyl, iso-pentyl,tert-butyl, n-pentyl, neopentyl, n-hexyl, sec-hexyl, n-heptyl, n-octyl,n-decyl, n-undecyl, dodecyl, and the like.

The term “alkenyl,” as used herein, denotes a monovalent group derivedfrom a straight- or branched-chain aliphatic moiety having at least onecarbon-carbon double bond by the removal of a single hydrogen atom.Unless otherwise specified, alkenyl groups contain 2-12 carbon atoms. Incertain embodiments, alkenyl groups contain 2-8 carbon atoms. In certainembodiments, alkenyl groups contain 2-6 carbon atoms. In someembodiments, alkenyl groups contain 2-5 carbon atoms, in someembodiments, alkenyl groups contain 2-4 carbon atoms, in yet otherembodiments alkenyl groups contain 2-3 carbon atoms, and in yet otherembodiments alkenyl groups contain 2 carbon atoms. Alkenyl groupsinclude, for example, ethenyl, propenyl, butenyl, 1-methyl-2-buten-1-yl,and the like.

The term “alkynyl,” as used herein, refers to a monovalent group derivedfrom a straight- or branched-chain aliphatic moiety having at least onecarbon-carbon triple bond by the removal of a single hydrogen atom.Unless otherwise specified, alkynyl groups contain 2-12 carbon atoms. Incertain embodiments, alkynyl groups contain 2-8 carbon atoms. In certainembodiments, alkynyl groups contain 2-6 carbon atoms. In someembodiments, alkynyl groups contain 2-5 carbon atoms, in someembodiments, alkynyl groups contain 2-4 carbon atoms, in yet otherembodiments alkynyl groups contain 2-3 carbon atoms, and in yet otherembodiments alkynyl groups contain 2 carbon atoms. Representativealkynyl groups include, but are not limited to, ethynyl, 2-propynyl(propargyl), l-propynyl, and the like.

The term “carbocycle” and “carbocyclic ring” as used herein, refers tomonocyclic and polycyclic moieties wherein the rings contain only carbonatoms. Unless otherwise specified, carbocycles may be saturated,partially unsaturated or aromatic, and contain 3 to 20 carbon atoms.Representative carbocyles include cyclopropanc, cyclobutane,cyclopentane, cyclohexane, bicyclo[2,2,1]heptane, norbornene, phenyl,cyclohexene, naphthalene, spiro[4.5]decane,

The term “aryl” used alone or as part of a larger moiety as in“aralkyl”. “aralkoxy”, or “aryloxyalkyl”, refers to monocyclic andpolycyclic ring systems having a total of five to 20 ring members,wherein at least one ring in the system is aromatic and wherein eachring in the system contains three to twelve ring members. The term“aryl” may be used interchangeably with the term “aryl ring”. In certainembodiments of the present invention, “aryl” refers to an aromatic ringsystem which includes, but is not limited to, phenyl, naphthyl,anthracyl and the like, which may bear one or more substituents. Alsoincluded within the scope of the term “aryl”, as it is used herein, is agroup in which an aromatic ring is fused to one or more additionalrings, such as benzofuranyl, indanyl, phthalimidyl, naphthimidyl,phenanthridinyl, or tetrahydronaphthyl, and the like.

The terms “heteroaryl” and “heteroar-”, used alone or as part of alarger moiety, e.g., “heteroaralkyl”, or “heteroaralkoxy”, refer togroups having 5 to 14 ring atoms, preferably 5, 6, 9 or 10 ring atoms;having 6, 10, or 14 π electrons shared in a cyclic array; and having, inaddition to carbon atoms, from one to five heteroatoms. The term“heteroatom” refers to nitrogen, oxygen, or sulfur, and includes anyoxidized form of nitrogen or sulfur, and any quaternized form of a basicnitrogen. Heteroaryl groups include, without limitation, thienyl,furanyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl,oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl,thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolizinyl,purinyl, naphthyridinyl, benzofuranyl and pteridinyl. The terms“heteroaryl” and “heteroar-”, as used herein, also include groups inwhich a heteroaromatic ring is fused to one or more aryl,cycloaliphatic, or heterocyclyl rings, where the radical or point ofattachment is on the heteroaromatic ring. Nonlimiting examples includeindolyl, isoindolyl, benzothienyl, benzofuranyl, dibenzofuranyl,indazolyl, benzimidazolyl, benzthiazolyl, quinolyl, isoquinolyl,cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, 4H-quinolizinyl,carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl,tetrahydroquinolinyl, tetrahydroisoquinolinyl, andpyrido[2,3-b]-1,4-oxazin-3(4H)-one. A heteroaryl group may be mono- orbicyclic. The term “heteroaryl” may be used interchangeably with theterms “heteroaryl ring”, “heteroaryl group”, or “heteroaromatic”, any ofwhich terms include rings that are optionally substituted. The term“heteroaralkyl” refers to an alkyl group substituted by a heteroaryl,wherein the alkyl and heteroaryl portions independently are optionallysubstituted.

As used herein, the terms “heterocycle”, “heterocyclyl”, “heterocyclicradical”, and “heterocyclic ring” are used interchangeably and refer toa stable 5- to 7-membered monocyclic or 7- to 14-membered bicyclicheterocyclic moiety that is either saturated or partially unsaturated,and having, in addition to carbon atoms, one or more, preferably one tofour, heteroatoms, as defined above. When used in reference to a ringatom of a heterocycle, the term “nitrogen” includes a substitutednitrogen. As an example, in a saturated or partially unsaturated ringhaving 0-3 heteroatoms selected from oxygen, sulfur or nitrogen, thenitrogen may be N (as in 3,4-dihydro-2H-pyrrolyl), NH (as inpyrrolidinyl), or ⁺NR (as in N-substituted pyrrolidinyl).

A heterocyclic ring can be attached to its pendant group at anyheteroatom or carbon atom that results in a stable structure and any ofthe ring atoms can be optionally substituted. Examples of such saturatedor partially unsaturated heterocyclic radicals include, withoutlimitation, tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl,pyrrolidonyl, piperidinyl, pyrrolinyl, tetrahydroquinolinyl,tetrahydroisoquinolinyl, decahydroquinolinyl, oxazolidinyl, piperazinyl,dioxanyl, dioxolanyl, diazepinyl, oxazepinyl, thiazepinyl, morpholinyl,and quinuclidinyl. The terms “heterocycle”, “heterocyclyl”,“heterocyclyl ring”, “heterocyclic group”, “heterocyclic moiety”, and“heterocyclic radical”, are used interchangeably herein, and alsoinclude groups in which a heterocyclyl ring is fused to one or morearyl, heteroaryl, or cycloaliphatic rings, such as indolinyl,3H-indolyl, chromanyl, phenanthridinyl, or tetrahydroquinolinyl, wherethe radical or point of attachment is on the heterocyclyl ring. Aheterocyclyl group may be mono- or bicyclic. The term“heterocyclylalkyl” refers to an alkyl group substituted by aheterocyclyl, wherein the alkyl and heterocyclyl portions independentlyare optionally substituted.

As used herein, the term “partially unsaturated” refers to a ring moietythat includes at least one double or triple bond. The term “partiallyunsaturated” is intended to encompass rings having multiple sites ofunsaturation, but is not intended to include aryl or heteroarylmoieties, as herein defined.

As described herein, compounds of the invention may contain “optionallysubstituted” moieties. In general, the term “substituted”, whetherpreceded by the term “optionally” or not, means that one or morehydrogens of the designated moiety are replaced with a suitablesubstituent. Unless otherwise indicated, an “optionally substituted”group may have a suitable substituent at each substitutable position ofthe group, and when more than one position in any given structure may besubstituted with more than one substituent selected from a specifiedgroup, the substituent may be either the same or different at everyposition. Combinations of substituents envisioned by this invention arepreferably those that result in the formation of stable or chemicallyfeasible compounds. The term “stable”, as used herein, refers tocompounds that are not substantially altered when subjected toconditions to allow for their production, detection, and, in certainembodiments, their recovery, purification, and use for one or more ofthe purposes disclosed herein.

In some chemical structures herein, substituents are shown attached to abond which crosses a bond in a ring of the depicted molecule. This meansthat one or more of the substituents may be attached to the ring at anyavailable position (usually in place of a hydrogen atom of the parentstructure). In cases where an atom of a ring so substituted has twosubstitutable positions, two groups may be present on the same ringatom. When more than one substituent is present, each is definedindependently of the others, and each may have a different structure. Incases where the substituent shown crossing a bond of the ring is —R,this has the same meaning as if the ring were said to be “optionallysubstituted” as described in the preceding paragraph.

Suitable monovalent substituents on a substitutable carbon atom of an“optionally substituted” group are independently halogen;—(CH₂)₀₋₄R^(∘); —(CH₂)₀₋₄OR^(∘); —O—(CH₂)₀₋₄C(O)OR^(∘);—(CH₂)₀₋₄CH(OR^(∘))₂; —(CH₂)₀₋₄SR^(∘); —(CH₂)₀₋₄Ph, which may besubstituted with R^(∘); —(CH₂)₀₋₄O(CH₂)₀₋₁ Ph which may be substitutedwith R^(∘); —CH═CHPh, which may be substituted with R^(∘); —NO₂; —CN;—N₃; —(CH₂)₀₋₄N(R^(∘))₂; —(CH₂)₀₋₄N(R^(∘))C(O)R^(∘); —N(R^(∘))C(S)R^(∘);—(CH₂)₀₋₄N(R^(∘))C(O)NR^(∘) ₂; —N(R^(∘))C(S)NR^(∘) ₂;—(CH₂)₀₋₄N(R^(∘))C(O)OR^(∘); —N(R^(∘))N(R^(∘))C(O)R^(∘);—N(R^(∘))N(R^(∘))C(O)NR^(∘) ₂; —N(R^(∘))N(R^(∘))C(O)OR^(∘);—(CH₂)₀₋₄C(O)R^(∘); —C(S)R^(∘); —(CH₂)₀₋₄C(O)OR^(∘);—(CH₂)₀₋₄C(O)N(R^(∘))₂; —(CH₂)₀₋₄C(O)SR^(∘); —(CH₂)₀₋₄C(O)OSiR^(∘) ₃;—(CH₂)₀₋₄OC(O)R^(∘); —OC(O)(CH₂)₀₋₄SR^(∘), SC(S)SR^(∘); —(CH₂)₀₋₄SC(O)R^(∘); —(CH₂)₀₋₄C(O)NR^(∘) ₂; —C(S)NR^(∘) ₂; —C(S)SR^(∘);—SC(S)SR^(∘), —(CH₂)₀₋₄ OC(O)NR^(∘) ₂; —C(O)N(OR^(∘))R^(∘);—C(O)C(O)R^(∘); —C(O)CH₂C(O)R^(∘); —C(NOR^(∘))R^(∘); —(CH₂)₀₋₄SSR^(∘);—(CH₂)₀₋₄ S(O)₂R; —(CH₂)₀₋₄S(O)₂OR^(∘); —(CH₂)₀₋₄S(O)₂R^(∘); —S(O)NR^(∘)₂; —(CH₂)₀₋₄S(O)R^(∘); —N(R^(∘))S(O)₂NR^(∘) ₂; —N(R^(∘))S(O)₂R^(∘);—N(OR^(∘))R^(∘); —C(NH)NR^(∘) ₂; —P(O)₂R^(∘); —P(O)R^(∘) ₂; —OP(O)R^(∘)₂; —OP(O)(OR^(∘))₂; SiR^(∘) ₃; —(C₁₋₄ straight or branchedalkylene)O—N(R^(∘))₂; or —(C₁₋₄ straight or branchedalkylene)C(O)O—N(R^(∘))₂, wherein each R^(∘) may be substituted asdefined below and is independently hydrogen, C₁₋₈ aliphatic, —CH₂Ph,—O(CH₂)₀₋₁Ph, or a 5-6-membered saturated, partially unsaturated, oraryl ring having 0-4 heteroatoms independently selected from nitrogen,oxygen, and sulfur, or, notwithstanding the definition above, twoindependent occurrences of R^(∘), taken together with their interveningatom(s), form a 3-12-membered saturated, partially unsaturated, or arylmono- or polycyclic ring having 0-4 heteroatoms independently selectedfrom nitrogen, oxygen, and sulfur, which may be substituted as definedbelow.

Suitable monovalent substituents on R^(∘) (or the ring formed by takingtwo independent occurrences of R^(∘) together with their interveningatoms), are independently halogen, —(CH₂)₀₋₂R^(•), -(haloR^(•)),—(CH₂)₀₋₂OH, —(CH₂)₀₋₂ OR^(•), —(CH₂)₀₋₂CH(OR^(•))₂; —O(haloR^(•)), —CN,—N₃, —(CH₂)₀₋₂C(O)R^(•), —(CH₂)₀₋₂C(O)OH, —(CH₂)₀₋₂C(O)OR^(•),—(CH₂)₀₋₄C(O)N(R^(∘))₂; —(CH₂)₀₋₂SR^(•), —(CH₂)₀₋₂SH, —(CH₂)₀₋₂NH₂,—(CH₂)₀₋₂NHR^(•), —(CH₂)₀₋₂NR^(•) ₂, —NO₂, —SiR^(•), —OSiR^(•) ₃,—C(O)SR^(•), —(C₁₋₄ straight or branched alkylene)C(O)OR^(•), or—SSR^(•) wherein each R^(•) is unsubstituted or where preceded by “halo”is substituted only with one or more halogens, and is independentlyselected from C₁₋₄ aliphatic, —CH₂Ph, —O(CH₂)₀₋₁Ph, or a 5-6-memberedsaturated, partially unsaturated, or aryl ring having 0-4 heteroatomsindependently selected from nitrogen, oxygen, and sulfur. Suitabledivalent substituents on a saturated carbon atom of R^(∘) include ═O and═S.

Suitable divalent substituents on a saturated carbon atom of an“optionally substituted” group include the following: ═O, ═S, ═NNR*₂,═NNHC(O)R*, ═NNHC(O)OR*, ═NNHS(O)₂R*, ═NR*, ═NOR*, —O(C(R*₂))₂ ₃O—, or—S(C(R*₂))₂ ₃S—, wherein each independent occurrence of R* is selectedfrom hydrogen, C₁₋₆ aliphatic which may be substituted as defined below,or an unsubstituted 5-6-membered saturated, partially unsaturated, oraryl ring having 0-4 heteroatoms independently selected from nitrogen,oxygen, and sulfur. Suitable divalent substituents that are bound tovicinal substitutable carbons of an “optionally substituted” groupinclude: —O(CR*₂)₂₋₃O—, wherein each independent occurrence of R* isselected from hydrogen, C₁₋₆ aliphatic which may be substituted asdefined below, or an unsubstituted 5-6-membered saturated, partiallyunsaturated, or aryl ring having 0-4 heteroatoms independently selectedfrom nitrogen, oxygen, and sulfur.

Suitable substituents on the aliphatic group of R* include halogen,—R^(•), -(haloR^(•)), —OH, —OR^(•), —O(haloR^(•)), —CN, —C(O)OH,—C(O)OR^(•), —NH₂, —NHR^(•), —NR^(•) ₂, or —NO₂ wherein each R^(•) isunsubstituted or where preceded by “halo” is substituted only with oneor more halogens, and is independently C₁₋₄ aliphatic, —CH₂Ph,—O(CH₂)₀₋₁Ph, or a 5-6-membered saturated, partially unsaturated, oraryl ring having 0-4 heteroatoms independently selected from nitrogen,oxygen, and sulfur.

Suitable substituents on a substitutable nitrogen of an “optionallysubstituted” group include —R^(†), —NR^(†) ₂, —C(O)R^(†), —C(O)OR^(†),—C(O)C(O)R^(†), —C(O)CH₂C(O)R^(†), —S(O)₂R^(†), —S(O)₂NR^(†) ₂,—C(S)NR^(†) ₂, —C(NH)NR^(†) ₂, or —N(R^(†))S(O)₂R^(†); wherein eachR^(†) is independently hydrogen, C₁₋₆ aliphatic which may be substitutedas defined below, unsubstituted —OPh, or an unsubstituted 5-6-memberedsaturated, partially unsaturated, or aryl ring having 0-4 heteroatomsindependently selected from nitrogen, oxygen, and sulfur, or,notwithstanding the definition above, two independent occurrences ofR^(†), taken together with their intervening atom(s) form anunsubstituted 3-12-membered saturated, partially unsaturated, or arylmono- or bicyclic ring having 0-4 heteroatoms independently selectedfrom nitrogen, oxygen, and sulfur.

Suitable substituents on the aliphatic group of R^(†) are independentlyhalogen, —R^(•), -(haloR^(•)), —OH, —OR^(•), —O(haloR^(•)), —CN,—C(O)OH, —C(O)OR^(•), —NH₂, —NHR^(•), —NR^(•) ₂, or —NO₂, wherein eachR^(•) is unsubstituted or where preceded by “halo” is substituted onlywith one or more halogens, and is independently C₁₋₄ aliphatic, —CH₂Ph,—O(CH₂)₀₋₁Ph, or a 5-6-membered saturated, partially unsaturated, oraryl ring having 0-4 heteroatoms independently selected from nitrogen,oxygen, and sulfur.

As used herein, the term “catalyst” refers to a substance the presenceof which increases the rate of a chemical reaction, while not beingconsumed or undergoing a permanent chemical change itself.

“Tetradentate” refers to ligands having four sites capable ofcoordinating to a single metal center.

As used herein, the term “about” preceding one or more numerical valuesmeans the numerical value ±5%.

DETAILED DESCRIPTION OF THE INVENTION

Among other things, the present invention provides integrated processesthat enable simultaneous production of valuable chemicals or polymerswhile upgrading synthesis gas by increasing the hydrogen to carbonmonoxide ratio. These inventive processes represent significant economicand environmental improvements versus prior art methods that utilize thewater gas shift reaction for the production of H₂ and CO₂ from thereaction of CO and water. The integrated processes herein result inimproved carbon efficiency for processes based on coal or biomassgasification or steam methane reforming, while producing valuablecommodity chemicals instead of waste CO₂.

In a first aspect, the present invention provides integrated processesfor the conversion of biomass, coal or natural gas to synthesize gas andcommodity chemicals or polymers derived from epoxide carbonylation. Incertain embodiments, such methods comprise the steps of:

-   -   a) in a first reaction zone, contacting syngas derived from        gasification reactions with an epoxide in the presence of a        carbonylation catalyst thereby consuming carbon monoxide from        the syngas and producing an epoxide carbonylation product,    -   b) recovering an upgraded gas stream from the first reaction        zone wherein the upgraded gas stream has a higher hydrogen to        carbon monoxide ratio than the starting syngas stream,    -   c) in a second reaction zone, utilizing the upgraded gas stream        to conduct a second chemical process requiring a hydrogen to        carbon monoxide ratio higher than the ratio in the industrial        gas stream utilized in step (a).

A schematic of a process according to this aspect of the invention isshown in FIG. 1. The process begins with a gasifier unit which convertsbiomass, coal or other carbonaceous feedstocks into a synthesis gasstream 101. Gas stream 101 is directed to carbonylation reactor 200where it is brought into contact with an epoxide (fed to reactor 200 viastream 201). In reactor 200, the epoxide and carbon monoxide in thesyngas stream react in the presence of a carbonylation catalyst toproduce epoxide carbonylation products which are ultimately recoveredvia product stream P1. A hydrogen-enriched syngas stream 102 isrecovered from reactor 200 and fed to reactor 300 where it is consumedas the feedstock for Fischer Tropsch synthesis yielding FT products viaproduct stream P2. FIG. 1 also illustrates the prior art process whereinwater gas shift reactor 400 is utilized in place of carbonylationreactor 200. In this case, CO in the synthesis gas stream 101 isconverted to CO₂ and hydrogen in the usual fashion with CO₂ exiting viawaste stream W1.

In another aspect, the present invention provides integrated processesfor the conversion of syngas to hydrogen substantially free of carbonmonoxide. In certain embodiments, such methods comprise the steps of:

-   -   a) in a first reaction zone, contacting a syngas stream derived        from methane steam reforming with an epoxide in the presence of        a carbonylation catalyst thereby consuming carbon monoxide from        the syngas and producing an epoxide carbonylation product,    -   b) recovering an upgraded gas stream from the first reaction        zone wherein the upgraded gas comprises hydrogen that is        substantially free of carbon monoxide.

In a another aspect, the present invention provides integrated processesfor the conversion of methane into hydrogen. In certain embodiments,such methods comprise the steps of:

-   -   c) in a first reaction zone, contacting a syngas stream derived        from methane steam reforming with an epoxide in the presence of        a carbonylation catalyst thereby consuming carbon monoxide from        the syngas and producing an epoxide carbonylation product,    -   d) recovering an upgraded gas stream from the first reaction        zone wherein the upgraded gas stream has a higher hydrogen to        carbon monoxide ratio than the starting syngas stream, and    -   e) in a second reaction zone, utilizing the upgraded gas stream        to conduct a second chemical process requiring a hydrogen to        carbon monoxide ratio higher than the ratio in the industrial        gas stream utilized in step (a).

FIG. 2 shows a schematic of one embodiment of such a process. Withreference to that figure, a methane steam reforming reactor 102 which isfed with steam and methane to produce syngas stream 103. Gas stream 103is fed to carbonylation reactor 200 along with epoxide (via stream 201).The epoxide and carbon monoxide react in the presence of a carbonylationcatalyst in reactor 200 to produce product stream P1 containingcarbonylation products and a hydrogen-enriched gas stream 104. Thehydrogen enriched gas stream 104 can be used for known purposesrequiring hydrogen or hydrogen-rich syngas. For example, as shown inFIG. 2, gas stream 104 can optionally be fed to a chemical reactor whichconsumes hydrogen to make chemical products (e.g. ammonia orhydrogenated products), or to a fuel cell to produce electricitycollectively represented by reactor 500 and outputs P3 and V1. Asdescribed more fully below, in certain embodiments, carbonylationreactor 200 is operated under conditions such that essentially all ofthe carbon monoxide in syngas stream 103 is consumed, in which casestream 104 consists of substantially pure hydrogen. These embodimentshave the attractive feature of eliminating the need for a pressure swingadsorption unit (e.g. PSA 402) or related purification stages.

In another aspect, the present invention provides an integrated processfor the production of hydrogen and commodity chemicals derived from betalactone carbonylation.

In certain embodiments, such methods comprise the steps of:

-   -   a) in a first reaction zone, contacting syngas with a beta        propiolactone in the presence of a carbonylation catalyst        thereby consuming carbon monoxide from the syngas and producing        a succinic anhydride product,    -   b) recovering an upgraded gas stream from the first reaction        zone wherein the upgraded gas stream has a higher hydrogen to        carbon monoxide ratio than the starting syngas stream,    -   c) in a second reaction zone, utilizing the upgraded gas stream        to conduct a second chemical process requiring a hydrogen to        carbon monoxide ratio higher than the ratio in the industrial        gas stream utilized in step (a).

FIG. 3 shows a schematic of a process according to this embodiment. Asshown in FIG. 3, Syngas reactor 103 which is fed with appropriate inputsand produces syngas stream 103. Gas stream 103 is fed to carbonylationreactor 200 along with a beta lactone (via stream 202). The lactone andcarbon monoxide react in the presence of a carbonylation catalyst inreactor 202 to produce a succinic anhydride product along with gasstream 104 which is enriched in hydrogen relative to stream 103. Asshown, the succinic anhydride can optionally be fed to hydrogenationreactor 501 along with the hydrogen stream 104 and contacted underhydrogenation conditions to produce tetrahydrofuran (THF), 1,4butanediol (BDO), or gamma butyrolactone (GBL).

FIG. 4 shows a schematic of another embodiment of the invention wherethe syngas input is upgraded twice by utilizing two carbonylationstages. As shown in the figure, syngas is produced in gasifier 100 inthe usual fashion, the output syngas stream 101 is directed to firstcarbonylation reactor 200 where it is contacted with an epoxide and acarbonylation catalyst to produce a beta lactone product and hydrogenenriched synthesis gas stream 103. Both the beta lactone and the gasstream 103 are directed to a 2^(nd) carbonylation reactor 202 where theyare further reacted in the presence of a carbonylation catalyst (whichmay be the same or different from the catalyst in the 1^(st)carbonylation reactor) to produce a succinic anhydride product stream P3along with a hydrogen stream 105. As shown these streams may optionallybe combined in hydrogenation reactor 502 where the anhydride reacts withthe hydrogen to produce a product stream P4 containing products selectedfrom the group consisting of THF, BDO and GBL.

Having generally described the spirit of the methods encompassed by thepresent invention, the following sections provide additional detailsregarding the compositions of the feedstocks, process streams andproducts as well as appropriate process conditions and apparatus forpracticing the inventive processes.

I) Syngas Production

The methods described herein do not place any specific restrictions onthe method by which the syngas input is produced or on the specificcomposition of the syngas. The terms “synthesis gas” or “syngas” as usedherein refer to any gaseous mixture of carbon monoxide and hydrogen.Such mixtures are typically produced from a carbonaceous feedstock.Syngas production methods include gasification of coal or biomass andsteam reforming of methane or other gaseous or liquid hydrocarbons andsimilar processes.

In certain embodiments, the syngas stream fed to the carbonylationreactor in the methods described herein is characterized in that it hasan H₂ to CO ratio between about 0.4:1 and about 1.5:1. Such a range istypical for syngas from solids gasification which tends to producecarbon rich syngas. In certain embodiments, the syngas stream fed to thecarbonylation reactor is characterized in that it has an H₂ to CO ratioof 0.4:1, about 0.5:1, about 0.6:1, about 0.7:1, about 0.8:1, about 1:1,about 1.2:1, about 1.4:1, or about 1.5:1. In certain embodiments, thesyngas stream fed to the carbonylation reactor is characterized in thatit has an H₂ to CO ratio less than about 1.6:1, less than about 1.5:1,less than about 1.3:1, less than about 1.2:1, less than about 1.1:1,less than about 1:1, less than about 0.8:1, less than about 0.7:1, orless than about 0.6:1.

In certain embodiments, the syngas stream fed to the carbonylationreactor in the methods described herein is characterized in that it hasan H₂ to CO ratio between about 1.5:1 and about 3:1. Such a range istypical for steam reforming processes utilizing methane or other lightaliphatic feedstocks. In certain embodiments, the syngas stream fed tothe carbonylation reactor is characterized in that it has an H₂ to COratio of 1.5:1, about 1.6:1, about 1.8:1, about 2:1, about 2.4:1, about2.8:1, or about 3:1. In certain embodiments, the syngas stream fed tothe carbonylation reactor is characterized in that it has an H₂ to COratio than about 3:1, less than about 2.8:1, less than about 2.5:1, lessthan about 2.2:1, or less than about 2:1.

Syngas typically contains varying amounts of CO₂. In many catalyticprocesses the CO₂ must be removed prior to using the gas. This issue ismore acute in processes relying on biomass gasification since the highoxygen content of biobased feedstocks typically produces syngas withhigh CO₂ content (often 20% or more). The presence of CO₂ not onlypotentially compromises downstream catalytic processes, but its presencein the syngas stream means that any process steps (e.g. compression ordesulfurization) performed prior to removal of the CO₂ are lessefficient since the CO₂ dilutes the stream and therefore requires higherprocessing capacity. Unexpectedly, the applicants have discovered thatepoxide carbonylation reactions promoted by certain classes of catalystsdescribed below are tolerant of high levels of CO₂ in the syngas stream.

Therefore, in certain embodiments, the syngas stream fed to thecarbonylation reactor in the methods described herein is characterizedin that it contains CO₂. In certain embodiments, the syngas streamcontains between about 1 mole percent and about 30 mole percent CO₂. Incertain embodiments, the syngas stream contains between about 1 molepercent and about 5 mole percent CO₂, between about 5 mole percent andabout 10 mole percent CO₂, between about 10 mole percent and about 20mole percent CO₂, or between about 20 mole percent and about 40 molepercent CO₂.

Nevertheless, in some circumstances, it may be desirable to provide asyngas stream which contains little or no CO₂ to the carbonylation step.Therefore, in certain embodiments, the syngas stream fed to thecarbonylation reactor in the methods described herein is characterizedin that it contains little or no CO₂. In certain embodiments, the syngasstream fed to the carbonylation reactor contains less than about 2000ppm, less than about 1000 ppm, less than about 500 ppm, less than about200 ppm, less than about 100 ppm, less than about 50 ppm, less thanabout 25 ppm, or less than about 10 ppm CO₂.

Without being bound by theory or thereby limiting the scope of theclaimed invention, it is believed that the presence of sulfur compoundsin the syngas stream is deleterious to the epoxide carbonylationreactions described herein. Therefore in certain embodiments, the syngasstream fed to the carbonylation reactor is substantially free of sulfur.In certain embodiments, the syngas stream fed to the carbonylationreactor contains less than about 500 ppm, less than 200 ppm, less thanabout 100 ppm, less than about 50 ppm, less than about 40 ppm, or lessthan about 25 ppm sulfur. In certain embodiments, the syngas stream fedto the carbonylation reactor contains less than about 10 ppm, less thanabout 5 ppm, less than about 2 ppm, less than about 1 ppm, or less thanabout 0.5 ppm sulfur. In certain embodiments, the syngas stream fed tothe carbonylation reactor contains less than about 0.2 ppm, less thanabout 0.1 ppm, less than about 0.05 ppm, less than about 0.01 ppm, orless than about 0.001 ppm sulfur.

It will be appreciated by the skilled artisan that production of syngasis a mature technology which is capable of operating with a diversearray of feedstocks and that numerous process conditions and catalystsfor production of syngas are known in the art. Likewise apparatus andmethods for the handling and purification of syngas are well known. Assuch, the selection of appropriate feedstocks and process conditions toproduce syngas suitable for practice of the inventive methods describedherein will be apparent to the skilled artisan based on the teachingsand disclosure herein. The exact choice of feedstocks and processingmethods is likely to depend on the local availability of materials andprevailing economic conditions.

II) Carbonylation Reaction Conditions

As described above and in the classes and subclasses herein, theinventive methods comprise a step of contacting the syngas stream with acarbonylation catalyst in the presence of an epoxide or a beta lactone.Catalysts, conditions and processes for these carbonylation reactionsare well known in the art and can be employed in the methods describedherein.

For embodiments where the syngas is reacted with an epoxide, noparticular constraints are placed on the identity of the epoxide. Anyepoxide or mixture of epoxides may be used, though as a generalprinciple those epoxides lacking other reactive functional groups (forexample protic functional groups) are less desirable since there is anincreased likelihood for side reactions with use of such substrates.Also, given the large scale on which syngas production is typicallypracticed, there is a strong preference to utilize epoxides that areavailable in bulk as commodity chemicals.

In certain embodiments where the methods entail epoxide carbonylationreactions, the epoxide is selected from the group consisting of:ethylene oxide, propylene oxide, butylene oxide, 1-hexene oxide,epichlorohydrin, and esters or ethers of glycidol. In certainembodiments, the epoxide is selected from the group consisting ofethylene oxide and propylene oxide. In certain embodiments the epoxideis ethylene oxide. In certain embodiments the epoxide is propyleneoxide.

The catalytic insertion of CO into epoxides is known to yield severalpossible products the identity of which is influenced by the particularcatalyst utilized and the reaction conditions employed. In certainembodiments of the present invention comprising a step of carbonylatingan epoxide, the product of the carbonylation is selected from the groupconsisting of: a beta lactone, a 3-hydroxy propionic acid, a succinicanhydride (via double carbonylation) and polyesters comprising thealternating copolymer of the epoxide and CO.

In certain embodiments, carbonylation results in the formation of a betalactone by the general reaction:

Examples include:

-   -   propylene oxide+CO→beta butyrolactone

and

-   -   ethylene oxide+CO→beta propiolactone

Suitable catalysts and reaction conditions for effecting this reactionare disclosed in published PCT applications: WO2003/050154,WO2004/089923, WO2012/158573, WO2010/118128, WO2013/063191, andWO2014/008232; in U.S. Pat. Nos. 5,359,081 and 5,310,948 and in thepublication “Synthesis of beta-Lactones” J. AM. CHEM. SOC., vol. 124,2002, pages 1174-1175. The entirety of each of the preceding referencesis hereby incorporated herein by reference.

In certain embodiments, carbonylation results in the formation of apolyester by the general reaction:

Examples include propylene oxide+CO→poly(3-hydroxybutyrate)

and

-   -   ethylene oxide+CO→poly propiolactone

In certain embodiments where methods of the present invention include astep of carbonylative polymerization, the methods utilize catalystsand/or process conditions disclosed in published PCT applicationsWO2003/074585A1, WO2011/063309, or WO2014004858 each of which isincorporated herein by reference in its entirety.

In certain embodiments, epoxide carbonylation results in the formationof a succinic anhydride by insertion of two molecules of CO. Suchprocesses conform to the general reaction scheme:

Examples include propylene oxide+CO→methylsuccinic anhydride

and

-   -   ethylene oxide+CO→succinic anhydride

In certain embodiments, where methods of the present invention includedouble carbonylation of epoxides, the methods utilize catalysts and/orprocess conditions disclosed in published PCT applications WO2012/030619and WO2013/122905, and U.S. Pat. No. 8,481,756, each of which isincorporated by reference herein in its entirety.

As described above, certain embodiments of the present inventioncomprise a step of contacting a syngas stream with a beta lactone in thepresence of a carbonylation catalyst to yield a succinic anhydridederivative along with a hydrogen-enriched syngas stream. Such processesconform to the general reaction scheme:

The catalysts and/or process conditions disclosed in published PCTapplications WO2012/030619 and WO2013/122905, and U.S. Pat. No.8,481,756, can be utilized to perform such steps.

In certain embodiments, carbonylation catalysts utilized in the presentmethods comprise metal carbonyl complexes. In certain embodiments, thecatalysts comprise metal carbonyl complexes in combination with one ormore other components such as amines, nitrogen-containing heterocycles,Lewis acids, or metal complexes.

Typically, where a carbonylation catalyst utilized in methods hereincomprises a metal carbonyl, a single metal carbonyl compound isprovided, but in certain embodiments mixtures of two or more metalcarbonyl compounds are provided. (Thus, when a provided metal carbonylcompound “comprises”, e.g., a neutral metal carbonyl compound, it isunderstood that the provided metal carbonyl compound can be a singleneutral metal carbonyl compound, or a neutral metal carbonyl compound incombination with one or more additional metal carbonyl compounds.)Preferably, the provided metal carbonyl compound is capable ofring-opening an epoxide and facilitating the insertion of CO into theresulting metal carbon bond. Metal carbonyl compounds with thisreactivity are well known in the art and are used for laboratoryexperimentation as well as in industrial processes such ashydroformylation. Additional description of suitable metal carbonylcompounds is provided in Appendix I at the end of this specification.

As mentioned above, carbonylation catalysts useful for practicingmethods of the present invention may include one or more additionalcomponents in combination with a metal carbonyl compound. In certainembodiments, such additional components comprise organic bases such asoptionally substituted amines, guanidines, or amidines and the like. Incertain embodiments, such additional components comprise heterocyclessuch as optionally substituted pyridines, pyrimidines, imidazoles, andthe like. In certain embodiments, such additional components compriseneutral Lewis acids such as boranes, aluminum alkyls, TiCl₄, BF₃, andthe like. In certain embodiments, such additional components comprisecationic Lewis acids. Additional description of suitable cationic Lewisacids is provided in Appendix 11 at the end of this specification.

In certain embodiments, the carbonylation catalysts employed in methodsof the present invention comprise heterogeneous carbonylation catalysts.In certain embodiments, such heterogeneous catalysts comprise supportedmetal carbonyl compounds. In certain embodiments, carbonylationcatalysts and processes disclosed in WO 2013/063191 may be adapted foruse in methods of the present invention.

The methods of the present invention provide no specific limitations onthe reaction conditions utilized in the carbonylation step. Forpractical application on industrial scale, the carbonylation reactionwill typically be performed in a continuous or semi-continuous format.Where the carbonylation reaction is performed in a continuous fashion,it may be conducted in any suitable reactor format, such as plug flowreactors (PFRs), continuous stirred-tank reactors (CSTRs) or any hybridor combination of these. Though the carbonylation stage of the methodsherein is often described as a single step, it may in fact occur inmultiple steps such as within a series of continuous stirred tankreactors or a plug flow reactor fed by one or more CSTRs. Continuousoperation requires additional processing steps and suitable apparatus tocontinuously feed reactants, catalysts, solvents and the like as well asprovision to continuously withdraw carbonylation products, recycle thecatalyst and solvents, purge impurities, and the like. A detaileddescription of such processes and apparatus is outside the scope of thisdisclosure since the requisite knowledge is readily available to theskilled artisan. In certain embodiments, the continuous carbonylationprocesses described in published PCT applications WO 2010/118128 WO2012/030619 WO 2013/063191 WO 2013/122905 and WO 2014008232 are suitablefor practicing certain embodiments of the methods described herein.

The syngas will typically be fed to the carbonylation reactor at asuperatmospheric pressure. No particular limits are placed on thepressure utilized—as with similar processes the chosen operatingpressure will require balance of the reaction rate and selectivity at agiven pressure with the cost of the equipment required to operate atthat pressure. In certain embodiments, the syngas is provided to thecarbonylation reactor at a pressure from about 50 psi to about 5,000psi. If the source of the synthesis gas provides a gas stream at apressure lower than the desired pressure in the carbonylation step, thenthe methods will include an additional step of pressurizing the syngasstream prior to contacting it with the epoxide or beta lactone. Incertain embodiments, the carbonylation reactor is integrated with asyngas production source that outputs a pressurized source of syngas andthe carbonylation reactor is run at a pressure substantially the same asthe output from the syngas source.

In certain embodiments, the syngas is provided to the carbonylationreactor at a pressure sufficient to afford a carbon monoxide partialpressure within the reactor from about 0.5 atmospheres to about 350atmospheres. In certain embodiments, the carbon monoxide partialpressure ranges from about 5 to about 100 atmospheres. In certainembodiments, the carbon monoxide partial pressure ranges from about 10to about 50 atmospheres, from about 5 to about 20 atmospheres, fromabout 1 to about 10 atmospheres, or from about 25 to about 50atmospheres. In some embodiments, carbon monoxide partial pressurewithin the carbonylation reactor ranges from about 0.5 atmospheres toabout 10 atmospheres. In some embodiments, a carbon monoxide partialpressure within the carbonylation reactor ranges from about 0.5 to about50, from about 1 to about 10, from about 1 to about 50, from about 1 toabout 100, from about 10 to about 50, from about 10 to about 100, fromabout 50 to about 100, from about 50 to about 200, from about 100 toabout 200, from about 100 to about 250, from about 200 to about 300, orfrom about 200 to about 500 atmospheres. In some embodiments, a carbonmonoxide partial pressure within the carbonylation reactor is about 10atmospheres. In some embodiments, a carbon monoxide partial pressurewithin the carbonylation reactor is about 10, about 20, about 30, about40, about 50, about 100, about 150, or about 200 atmospheres.

In certain embodiment, the step of contacting the syngas stream withepoxide or beta lactone in the presence of a carbonylation catalyst isperformed under conditions such that the hydrogen-to-carbon monoxideratio in the upgraded syngas stream exiting the reactor is maintainedwithin a specific range. In certain embodiments, the desired range isdependent on the identity of the downstream process in which theupgraded gas stream is to be used. For integrated carbonylation-FischerTropsch processes, it is desirable to maintain the H₂ to CO ratio of theupgraded syngas stream around 2:1. For integratedcarbonylation-hydrogenation processes, it is desirable to maintain theH₂ to CO ratio at a high level, or even to consume substantially all ofthe CO in the syngas feed stream such that the upgraded stream containslittle or no CO. Therefore, in certain embodiments methods of thepresent invention are characterized in that the upgraded syngas streamobtained from the carbonylation reactor has an H₂ to CO ratio aboveabout 2:1. In certain embodiments, the upgraded syngas stream obtainedfrom the carbonylation reactor has an H₂ to CO ratio above about 2.1:1,above about 2.2:1, above about 2.3:1, above about 2.4:1, above about2.1:1, above about 2.1:1, above about 2.1:1, above about 2.1:1, aboveabout 2.5:1, above about 2.8:1, above about 3:1, above about 3.5:1,above about 4:1, above about 5:1, or above about 10:1. In certainembodiments, the upgraded syngas stream obtained from the carbonylationreactor has an H₂ to CO ratio above about 2.1:1, above about 10:1, aboveabout 20:1, above about 50:1, above about 100:1, above about 200:1,above about 500:1, or above about 1000:1.

In certain embodiments methods of the present invention arecharacterized in that the upgraded syngas stream obtained from thecarbonylation reactor has an H₂ to CO ratio of about 2:1. In certainembodiments, the upgraded syngas stream obtained from the carbonylationreactor has an H₂ to CO ratio of about 2.1:1, about 2.2:1, about 2.5:1,about 3:1, about 4:1, about 5:1, or about 10:1.

In certain embodiments methods of the present invention arecharacterized in that the upgraded syngas stream obtained from thecarbonylation reactor is essentially free of CO. In certain embodiments,the upgraded syngas stream obtained from the carbonylation reactorcontains less than 2%, less than 1%, less than 0.5%, less than 0.2%, orless than 0.1% CO. In certain embodiments, the upgraded syngas streamobtained from the carbonylation reactor contains less than 500 ppm, lessthan 400 ppm, less than 200 ppm, less than 100 ppm, less than 50 ppm,less than 25 ppm, less than 10 ppm, less than 5 ppm, or less than 1 ppmCO.

III) Utilization of the Upgraded Syngas Stream

The upgraded syngas stream from the carbonylation reactor may berecovered and handled by any suitable means. Typically the upgradedsyngas stream will exit the carbonylation reactor via a gas vent, aback-pressure regulator or an outlet port which may include provisionfor liquids separation, recompression, scrubbing, drying, chilling orheating, and the like as is typically performed in industry. In certainembodiments, the carbonylation reactor is operated at a higher pressurethan the downstream process fed with the upgraded syngas stream thatexits the carbonylation reactor. This has the advantage of not requiringrecompression of the upgraded syngas stream. Nonetheless, this is notalways possible if the downstream process is one that requires highhydrogen partial pressures. In this case, the methods of the presentinvention will include a step of compressing the upgraded syngas streamprior to utilizing it in next process.

In certain embodiments, the upgraded syngas stream exiting thecarbonylation reactor will contain impurities that must be removed priorto utilization of the upgraded stream. For example, if the streamcontains carbon dioxide and the downstream process is not tolerant ofCO₂, then the methods necessarily require an intermediate step to scrubCO₂ from the upgraded stream. Such methods are well known in the art andmay include membrane separation, pressure swing adsorption, chemicaladsorption, cryotreatment and the like. In certain embodiments, volatileresidues from the carbonylation reactor may be present in the upgradedsyngas stream. Such residues may include solvent, unreacted epoxide,carbonylation side products such as acetaldehyde, volatile metalcarbonyl residues and the like. In certain embodiments, the upgradedsyngas stream is treated to remove such impurities prior to utilizationof the stream in a downstream process. In certain embodiments where thedownstream process is tolerant of such residues, it may be preferable toleave the impurities in the upgraded syngas stream and purge them at alater stage in the process.

As described above a feature of some methods of the present invention isthe use of the upgraded syngas stream in a downstream process.Preferably, the carbonylation stage of the methods increases the H₂:COratio in the stream to a range that is desirable for the downstreamprocess.

In certain embodiments, the downstream process comprises Fischer-Tropsch(FT) synthesis. FT technology is a mature field and appropriateoperating conditions, apparatus, catalysts and product isolationtechniques for FT processes are well known in the art. The skilledartisan utilizing the wealth of knowledge available in the FT field,together with the teachings herein, will readily apprehend suitableconfigurations for the FT step described in methods herein. An overviewof FT technology is provided in Advance Catalysis. Volume 186, pp 3-12,the entirety of which is incorporated herein by reference.

In certain embodiments the downstream process in which the upgradedsyngas stream is utilized is an FT gas-to-liquid process for theproduction of fuels and/or chemicals such as olefins and/or alcohols. Incertain embodiments, the downstream process in which the upgraded syngasstream is utilized is a Low Temperature FT synthesis (LTFT). In certainembodiments, the downstream process in which the upgraded syngas streamis utilized is a High Temperature FT synthesis (HTFT). The FischerTropsch reactor in which the upgraded syngas stream is utilized may beof any known configuration. Suitable configurations include multitubularfixed bed reactors, entrained flow reactors, slurry reactors, bubblereactors, fluidized bed reactors, and riser reactors. Likewise, anyknown FT catalyst system may be employed in the present methods.Suitable catalysts include, but are not limited to: cobalt, iron,ruthenium, nickel, and any combination of two or more of these. The FTcatalysts may include additional components as are known in the artincluding alkaki metals, copper, manganese, lanthanide metals orcompounds, actinide metals or compounds, alumina, zirconia, and thelike.

In certain embodiments the downstream process in which the upgradedsyngas stream is utilized is a process for the production of methane.Suitable catalysts and conditions for methane synthesis from syngas areknown in the art and the skilled artisan utilizing the teachings hereinwith the known art will apprehend suitable conditions, apparatus andcatalyst systems to effect the conversion of the upgraded syngas streamto methane.

In certain embodiments the downstream process in which the upgradedsyngas stream is utilized is a process for the production of methanol.Suitable catalysts and conditions for methanol synthesis from syngas areknown in the art and the skilled artisan utilizing the teachings hereinwith the known art will apprehend suitable conditions, apparatus andcatalyst systems to effect the conversion of the upgraded syngas streamto methanol.

In certain embodiments the downstream process in which the upgradedsyngas stream is utilized is a process for the production of dimethylether. Suitable catalysts and conditions for methanol synthesis fromsyngas are known in the art and the skilled artisan utilizing theteachings herein with the known art will apprehend suitable conditions,apparatus and catalyst systems to effect the conversion of the upgradedsyngas stream to methanol.

In other embodiments, the integrated upgraded syngas stream is utilizedas a fuel. For example, the upgraded syngas stream can be fed to a fuelcell, combusted in a turbine or boiler, or used to fuel an internalcombustion engine. Therefore, depending on the process utilized,processes of the present invention may provide an output comprisingsteam, thermal energy, electrical energy, or mechanical energy. Due tothe higher H₂ to CO ratio in the upgraded gas stream, the upgradedstream may have a higher energy content than the starting syngas stream(it will be appreciated that whether or not this is the case will dependon the amount of other gasses such as CO₂ that may also be present inthe streams).

IV) Integrated Production of FT Products and EO Carbonylation Products

As described above, in certain embodiments, the present inventionencompasses methods for the integrated production of chemicals fromsyngas derived from gasification.

In certain embodiments, such processes produce as final outputs, betapropiolactone or polypropiolactone (or derivatives of these such asacrylic acid, acrylate esters or superabsorbent polymers) by ethyleneoxide carbonylation and FT products such as liquid fuels and relatedchemicals.

In certain embodiments, methods of the present invention comprise thesteps of:

-   -   a) gasifying a carbonaceous solid to provide a syngas stream        having an H₂ to CO ratio in the range from about 0.4:1 to about        1.2:1;    -   b) feeding this syngas stream to an epoxide carbonylation        reactor where the syngas stream is contacted with ethylene oxide        in the presence of a carbonylation catalyst to deplete the        syngas of at least a portion of its CO content and provide a        carbonylation product selected from the group consisting of:        beta propiolactone, and polypropiolactone;    -   c) recovering an upgraded syngas stream from the carbonylation        reactor characterized in that the upgraded stream has a higher        H₂ to CO ratio than the syngas stream provided by step (a); and    -   d) feeding the upgraded syngas stream to a Fischer Tropsch        reactor to produce a product selected from the group consisting        of: liquid fuels, oils, waxes, olefins, alcohols, and any        combination of two or more of these.

In certain embodiments, step (a) of the method above comprises coalgasification. In certain embodiments, such methods are characterized inthat the syngas stream in step (a) has an H₂ to CO ratio of from about0.6:1 to about 0.8:1. In certain embodiments, such methods arecharacterized in that the syngas stream in step (a) has an H₂ to COratio of about 0.7:1.

In certain embodiments, step (a) of the method above comprises biomassgasification. In certain embodiments, the biomass is selected from thegroup consisting of: corn stover, sugar cane bagasse, switch grass,municipal solid waste, and wood waste. In certain embodiments, suchmethods are characterized in that the syngas stream in step (a) has anH2 to CO ratio of from about 0.4:1 to about 0.8:1. In certainembodiments, such methods are characterized in that the syngas stream instep (a) has an H₂ to CO ratio of about 0.6:1. In certain embodiments,such methods are characterized in that the syngas stream in step (a) hasan H₂ to CO ratio of about 0.5:1.

In certain embodiments, the method above comprises an additional step ofcompressing the syngas stream prior to feeding it to the carbonylationreactor. In certain embodiments, the method above comprises anadditional step of removing nitrogenous and sulfurous compounds from thesyngas stream prior to feeding it to the carbonylation reactor. Incertain embodiments, the method above comprises an additional step ofdrying the syngas stream prior to feeding it to the carbonylationreactor. In certain embodiments, the method above comprises anadditional step of removing CO₂ from the syngas stream prior to feedingit to the carbonylation reactor. In certain embodiments, the methodabove is characterized in that CO₂ is not removed from the syngas streamprior to feeding it to the carbonylation reactor.

In certain embodiments, the product of step (b) of the method abovecomprises beta propiolactone and the method comprises an additional stepof converting the beta propiolactone to acrylic acid, or acrylateesters.

In certain embodiments, the product of step (b) of the method abovecomprises beta propiolactone and the method comprises an additional stepof converting the beta propiolactone to succinic anhydride. In certainembodiments such methods comprise an additional step of converting thesuccinic anhydride to a product selected from the group consisting of:succinic acid, 1,4 butanediol, tetrahydrofuran, gamma butyrolactone, orany combination of two or more of these.

In certain embodiments where the method above comprises an additionalstep of converting beta propiolactone to succinic anhydride, theconversion is conducted in a second carbonylation reactor. In certainembodiments, the second carbonylation reactor is also fed with thesyngas stream produced in step (a) where it is contacted with the betapropiolactone in the presence of a carbonylation catalyst to deplete thesyngas of at least a portion of its CO content and provide succinicanhydride as a second carbonylation product. In certain embodiments, asecond upgraded syngas stream, characterized in that it has a higher H₂to CO ratio that the syngas stream produced in step (a) is recoveredfrom the second carbonylation reactor. In certain embodiments, the firstand second upgraded syngas streams are combined and utilized in step(d).

In certain embodiments where the method above comprises an additionalstep of converting beta propiolactone to succinic anhydride, theconversion is conducted in a second carbonylation reactor which is fedwith the upgraded syngas stream produced in step (b) where it iscontacted with the beta propiolactone in the presence of a carbonylationcatalyst to further deplete the upgraded syngas stream of its CO therebyproviding a twice-upgraded syngas stream having a higher H₂ to CO ratiothan the upgraded syngas stream from step (c). In certain embodiments,the method comprises an additional step of recovering the twice upgradedsyngas stream from the second carbonylation reactor and feeding it tothe FT reactor in step (d).

In certain embodiments, the product of step (b) of the method abovecomprises polypropiolactone and the method comprises an additional stepof pyrolyzing the polypropiolactone to produce acrylic acid.

In certain embodiments, the carbonylation catalyst in step (b) of themethod above comprises a metal carbonyl compound. In certainembodiments, the metal carbonyl compound is selected from any of thosedescribed in Appendix I. In certain embodiments, the metal carbonylcompound comprises a cobalt carbonyl compound. In certain embodiments,metal carbonyl compound comprises a rhodium carbonyl compound. Incertain embodiments, the carbonylation catalyst in step (b) of themethod above comprises a metal carbonyl compound in combination withanother component selected from the group consisting of: organic bases,neutral Lewis acids, and cationic Lewis acids. In certain embodiments,the carbonylation catalyst in step (b) of the method above comprises ananionic cobalt carbonyl compound in combination with a cationic Lewisacid. In certain embodiments, such cationic Lewis acids comprise metalligand complexes. In certain embodiments, the metal ligand complexescomprise any complex described in Appendix II. In certain embodiments,such metal ligand complexes comprise a metal atom coordinated to amultidentate ligand. In certain embodiments, such metal ligand complexescomprise an aluminum or chromium atom. In certain embodiments, suchmetal ligand complexes comprise a porphyrin or salen ligand. In certainembodiments, the carbonylation catalyst in step (b) of the method abovecomprises any combination of a metal carbonyl compound from Appendix Iand a metal complex from Appendix II.

In certain embodiments, step (c) in the method above is characterized inthat the upgraded syngas stream recovered has an H₂ to CO ratio betweenabout 1.2:1 and about 3:1. In certain embodiments, the upgraded syngasstream recovered has an H, to CO ratio between about 1.6:1 and about2.8:1, between about 1.8:1 and about 2.6:1, between about 1.8:1 andabout 2.2:1, or between about 1.9:1 and about 2.1:1. In certainembodiments, the upgraded syngas stream recovered has an H₂ to CO ratioof about 2:1.

In certain embodiments, the method above is characterized in that thereaction pressure in the carbonylation reactor is higher than thereaction pressure in the FT reactor. In certain embodiments, theupgraded syngas stream is fed to the FT reactor without an intermediatecompression step. In certain embodiments, the upgraded syngas streamexits the carbonylation reactor via a backpressure regulator and is feddirectly to the FT reactor.

In certain embodiments, the method above is characterized in that theupgraded syngas stream is treated to remove one or more components priorto feeding the stream to the FT reactor. In certain embodiments, theupgraded syngas stream is treated to remove residual solvent prior tofeeding the stream to the FT reactor. In certain embodiments, theupgraded syngas stream is treated to remove residual epoxide prior tofeeding the stream to the FT reactor. In certain embodiments, theupgraded syngas stream is treated to remove carbon dioxide prior tofeeding the stream to the FT reactor.

In certain embodiments, the method above is characterized in that the FTreactor in step (d) is a Low Temperature FT synthesis (LTFT) reactor. Incertain embodiments, the downstream process in which the upgraded syngasstream is utilized is a High Temperature FT synthesis (HTFT) reactor.

In certain embodiments, the method above is characterized in that theoverall process has a carbon efficiency greater than 50%. That is, atleast 50% of the carbon atoms fed to the gasification reactor arecontained in the combined products from the EO carbonylation reactor andthe FT reactor. In certain embodiments, the method is characterized inthat the overall process has a carbon efficiency greater than 55%,greater than 60%, greater than 62%, greater than 63%, greater than 64%,or greater than 65%. In certain embodiments, the method is characterizedin that the overall process has a carbon efficiency greater than 66%,greater than 67%, greater than 68%, greater than 69%, or greater than70%. In certain embodiments, the method is characterized in that theoverall process has a carbon efficiency between about 50% and about 60%.In certain embodiments, the method is characterized in that the overallprocess has a carbon efficiency between about 55% and about 60%. Incertain embodiments, the method is characterized in that the overallprocess has a carbon efficiency between about 60% and about 64%. Incertain embodiments, the method is characterized in that the overallprocess has a carbon efficiency between about 64% and about 67%. Incertain embodiments, the method is characterized in that the overallprocess has a carbon efficiency between about 67% and about 70%.

In certain embodiments, the method above is characterized in that the FTprocess in step (d) is fed with syngas from the gasification process instep (a) without utilizing the water gas shift reaction to increase itsH₂ to CO ratio.

V) Integrated Production of EO Carbonylation Products and Purificationof Hydrogen

As described above, in certain embodiments, the present inventionencompasses methods for the integrated production of chemicals andpurified hydrogen.

In certain embodiments, such processes produce as final outputs, betapropiolactone or polypropiolactone (or derivatives of these such asacrylic acid, acrylate esters or superabsorbent polymers) by ethyleneoxide carbonylation and hydrogen or products of hydrogen such aselectrical energy, ammonia, or hydrogenated chemicals.

In certain embodiments, methods of the present invention comprise thesteps of:

-   -   a) producing a syngas stream by gasification or reforming        technologies;    -   b) feeding this syngas stream to an epoxide carbonylation        reactor where the syngas stream is contacted with ethylene oxide        in the presence of a carbonylation catalyst to deplete the        syngas of at least a portion of its CO content and provide a        carbonylation product selected from the group consisting of:        beta propiolactone, and polypropiolactone; and    -   c) recovering a hydrogen stream from the carbonylation reactor        characterized in that the hydrogen stream has a higher H₂ to CO        ratio than the syngas stream provided by step (a).

In certain embodiments, step (a) of the method above comprises steammethane reforming. In certain embodiments, such methods arecharacterized in that the syngas stream in step (a) has an H₂ to COratio of from about 2.8:1 to about 3.2:1. In certain embodiments, suchmethods are characterized in that the syngas stream in step (a) has anH₂ to CO ratio of about 3:1.

In certain embodiments, the method above comprises an additional step ofcompressing the syngas stream prior to feeding it to the carbonylationreactor. In certain embodiments, the method above comprises anadditional step of removing sulfurous compounds from the syngas streamprior to feeding it to the carbonylation reactor. In certainembodiments, the method above comprises an additional step of drying thesyngas stream prior to feeding it to the carbonylation reactor. Incertain embodiments, the method above comprises an additional step ofremoving CO₂ from the syngas stream prior to feeding it to thecarbonylation reactor. In certain embodiments, the method above ischaracterized in that CO₂ is not removed from the syngas stream prior tofeeding it to the carbonylation reactor.

In certain embodiments, the product of step (b) of the method abovecomprises beta propiolactone and the method comprises an additional stepof converting the beta propiolactone to acrylic acid, or acrylateesters.

In certain embodiments, the product of step (b) of the method abovecomprises polypropiolactone and the method comprises an additional stepof pyrolyzing the polypropiolactone to produce acrylic acid.

In certain embodiments, the carbonylation catalyst in step (b) of themethod above comprises a metal carbonyl compound. In certainembodiments, the metal carbonyl compound is selected from any of thosedescribed in Appendix I. In certain embodiments, the metal carbonylcompound comprises a cobalt carbonyl compound. In certain embodiments,metal carbonyl compound comprises a rhodium carbonyl compound. Incertain embodiments, the carbonylation catalyst in step (b) of themethod above comprises a metal carbonyl compound in combination withanother component selected from the group consisting of: organic bases,neutral Lewis acids, and cationic Lewis acids. In certain embodiments,the carbonylation catalyst in step (b) of the method above comprises ananionic cobalt carbonyl compound in combination with a cationic Lewisacid. In certain embodiments, such cationic Lewis acids comprise metalligand complexes. In certain embodiments, the metal ligand complexescomprise any complex described in Appendix II. In certain embodiments,such metal ligand complexes comprise a metal atom coordinated to amultidentate ligand. In certain embodiments, such metal ligand complexescomprise an aluminum or chromium atom. In certain embodiments, suchmetal ligand complexes comprise a porphyrin or salen ligand. In certainembodiments, the carbonylation catalyst in step (b) of the method abovecomprises any combination of a metal carbonyl compound from Appendix Iand a metal complex from Appendix II.

In certain embodiments, the method above is characterized in that thehydrogen stream recovered in step (c) has an H₂ to CO ratio betweenabout 4:1 and about 1,000:1. In certain embodiments, the upgraded syngasstream recovered has an H₂ to CO ratio between about 5:1 and about 10:1,between about 10:1 and about 50:1, between about 50:1 and about 100:1,or between about 100:1 and about 1000:1. In certain embodiments, thehydrogen stream contains essentially no CO.

In certain embodiments, the method above is characterized in that thehydrogen stream is treated to remove one or more components prior touse. In certain embodiments, the hydrogen stream is treated to removeresidual solvent prior to use. In certain embodiments, the hydrogenstream is treated to remove residual epoxide prior to use. In certainembodiments, the hydrogen stream is treated to remove carbon dioxideprior to use.

In certain embodiments, the method above is characterized in that thehydrogen stream is utilized on site for a process selected from: ammoniasynthesis, powering a fuel cell, hydrogenation, and any combination oftwo or more of these. In certain embodiments, the hydrogen is compressedand distributed for use elsewhere.

In certain embodiments, the method above is characterized in that theoverall process has a carbon efficiency greater than 50%. That is, atleast 50% of the carbon atoms fed to the steam reforming reactor arecontained in products from the EO carbonylation reactor. In certainembodiments, the method is characterized in that the overall process hasa carbon efficiency greater than 55%, greater than 60%, greater than62%, greater than 63%, greater than 64%, or greater than 65%. In certainembodiments, the method is characterized in that the overall process hasa carbon efficiency greater than 66%, greater than 67%, greater than68%, greater than 69%, or greater than 70%. In certain embodiments, themethod is characterized in that the overall process has a carbonefficiency between about 50% and about 60%. In certain embodiments, themethod is characterized in that the overall process has a carbonefficiency between about 55% and about 60%. In certain embodiments, themethod is characterized in that the overall process has a carbonefficiency between about 60% and about 64%. In certain embodiments, themethod is characterized in that the overall process has a carbonefficiency between about 64% and about 67%. In certain embodiments, themethod is characterized in that the overall process has a carbonefficiency between about 67% and about 70%.

VI) Integrated Production of Hydrogen and C4 Chemical Products

In certain embodiments, the present invention encompasses methods forthe integrated production of C4 chemicals and hydrogen.

In certain embodiments, such processes produce as final outputs,succinic anhydride (or derivatives of succinic anhydride such assuccinic acid, 1,4-butanediol. THF and gamma butyrolactone) and hydrogenor products of hydrogen such as electrical energy, ammonia, orhydrogenated chemicals.

In certain embodiments, methods of the present invention comprise thesteps of:

-   -   d) producing a syngas stream by steam reforming of methane or        other lower aliphatic compounds;    -   e) feeding this syngas stream to a carbonylation reactor where        the syngas stream is contacted with a substrate selected from        ethylene oxide, beta propiolactone and combinations of these, in        the presence of a carbonylation catalyst to deplete the syngas        of at least a portion of its CO content and provide succinic        anhydride as a carbonylation product; and    -   f) recovering a hydrogen stream from the carbonylation reactor        characterized in that the hydrogen stream has a higher H₂ to CO        ratio than the syngas stream provided by step (a).

In certain embodiments, step (a) of the method above comprises steammethane reforming. In certain embodiments, such methods arecharacterized in that the syngas stream in step (a) has an H₂ to COratio of from about 2.8:1 to about 3.2:1. In certain embodiments, suchmethods are characterized in that the syngas stream in step (a) has anH₂ to CO ratio of about 3:1.

In certain embodiments, the method above comprises an additional step ofcompressing the syngas stream prior to feeding it to the carbonylationreactor. In certain embodiments, the method above comprises anadditional step of removing sulfurous compounds from the syngas streamprior to feeding it to the carbonylation reactor. In certainembodiments, the method above comprises an additional step of drying thesyngas stream prior to feeding it to the carbonylation reactor. Incertain embodiments, the method above comprises an additional step ofremoving CO₂ from the syngas stream prior to feeding it to thecarbonylation reactor. In certain embodiments, the method above ischaracterized in that CO₂ is not removed from the syngas stream prior tofeeding it to the carbonylation reactor.

In certain embodiments, step (b) of the method above comprises doublecarbonylation of ethylene oxide to produce the succinic anhydride. Incertain embodiments, the double carbonylation proceeds in the presenceof a single carbonylation catalyst, while in other embodiments, thedouble carbonylation proceeds with the aid of two or more separatecatalysts.

In certain embodiments, the double carbonylation of ethylene oxideoccurs in a single reactor, while in other embodiments, the twocarbonylation steps occur in the two or more reactors. The utilizationof two reactors is advantageous in certain embodiments, because of thekinetics of the two carbonylation steps. Without being bound by theoryor thereby limiting the scope of the present invention, it is believedthat carbonylation of ethylene oxide to produce beta lactones is zeroorder in epoxide concentration (i.e. the rate of EO conversion isindependent of EO concentration. Therefore, it is believed that acontinuous EO carbonylation reactor can be operated efficiently understeady state conditions and maintain a low concentration of EO in theproduct stream. Conversely, it is believed that the carbonylation ofbeta lactones is not zero order in lactone and the reaction rate issensitive to lactone concentration. Therefore, to achieve highconversion in carbonylation of lactones it is believed this step is bestperformed under plug flow conditions so that a significant proportion ofthe lactone is consumed. Therefore, in certain embodiments of the methoddescribed above, the conversion of ethylene oxide to succinic anhydrideoccurs in two or more reactors. In certain embodiments, the reactors areoperated under different conditions to maximize the efficiency of eachof the two carbonylation steps. In certain embodiments ethylene oxide iscontacted with the syngas stream in a first carbonylation reactor toprovide beta propiolactone as an intermediate product which is fed to asecond carbonylation reactor where it is converted to succinicanhydride. In certain embodiments of such methods, the firstcarbonylation reactor is a steady state reactor. In certain embodiments,the second reactor is a plug flow reactor. In certain embodiments ofsuch methods, the first carbonylation reactor is a steady state reactorand the second reactor is a plug flow reactor. In certain embodiments,the second carbonylation reactor is fed with an upgraded syngas streamrecovered from the first carbonylation reactor where the upgraded syngasstream has a higher H₂ to CO ratio than the syngas stream produced instep (a).

In other embodiments where the carbonylation occurs in two or morereactors, each of two carbonylation reactors is fed with the syngasstream from step (a). In certain embodiments, a hydrogen stream isobtained from each of the carbonylation reactors. In certain embodimentswhere multiple hydrogen streams are obtained from two or more reactors,they are combined. In other embodiments, each of the streams is usedseparately.

In certain embodiments, the carbonylation catalyst in step (b) of themethod above comprises a metal carbonyl compound. In certainembodiments, the metal carbonyl compound is selected from any of thosedescribed in Appendix I. In certain embodiments, the metal carbonylcompound comprises a cobalt carbonyl compound. In certain embodiments,metal carbonyl compound comprises a rhodium carbonyl compound. Incertain embodiments, the carbonylation catalyst in step (b) of themethod above comprises a metal carbonyl compound in combination withanother component selected from the group consisting of: organic bases,neutral Lewis acids, and cationic Lewis acids. In certain embodiments,the carbonylation catalyst in step (b) of the method above comprises ananionic cobalt carbonyl compound in combination with a cationic Lewisacid. In certain embodiments, such cationic Lewis acids comprise metalligand complexes. In certain embodiments, the metal ligand complexescomprise any complex described in Appendix II. In certain embodiments,such metal ligand complexes comprise a metal atom coordinated to amultidentate ligand. In certain embodiments, such metal ligand complexescomprise an aluminum or chromium atom. In certain embodiments, suchmetal ligand complexes comprise a porphyrin or salen ligand. In certainembodiments, the carbonylation catalyst in step (b) of the method abovecomprises any combination of a metal carbonyl compound from Appendix Iand a metal complex from Appendix 11.

In certain embodiments, the method above is characterized in that thehydrogen stream recovered in step (c) has an H₂ to CO ratio betweenabout 4:1 and about 1,000:1. In certain embodiments, the upgraded syngasstream recovered has an H₂ to CO ratio between about 5:1 and about 10:1,between about 10:1 and about 50:1, between about 50:1 and about 100:1,or between about 100:1 and about 1000:1. In certain embodiments, thehydrogen stream contains essentially no CO.

In certain embodiments, the method above is characterized in that thehydrogen stream is treated to remove one or more components prior touse. In certain embodiments, the hydrogen stream is treated to removeresidual solvent prior to use. In certain embodiments, the hydrogenstream is treated to remove residual epoxide prior to use. In certainembodiments, the hydrogen stream is treated to remove carbon dioxideprior to use.

In certain embodiments, the method above is characterized in that thehydrogen stream is utilized on site for a process selected from: ammoniasynthesis, powering a fuel cell, hydrogenation, and any combination oftwo or more of these. In certain embodiments, the hydrogen is compressedand distributed for use elsewhere.

In certain embodiments, the hydrogen stream is utilized forhydrogenation of the succinic anhydride produced in step (b). In certainembodiments, the hydrogenation of succinic anhydride from step (b) withthe hydrogen stream from step (c) produces 1,4-butanediol. In certainembodiments, the hydrogenation of succinic anhydride from step (b) withthe hydrogen stream from step (c) produces THF. In certain embodiments,the hydrogenation of succinic anhydride from step (b) with the hydrogenstream from step (c) produces gamma butyrolactone. Methods and catalystsfor conversion of maleic and succinic anhydride or their correspondingacids to the products 1,4-BDO. THF and GBL are known in the art and canbe adapted by the skilled artisan to serve in the present methods.

In certain embodiments, the method above is characterized in that theoverall process has a carbon efficiency greater than 50%. That is, atleast 50% of the carbon atoms fed to the steam reforming reactor arecontained in products from the EO carbonylation reactor. In certainembodiments, the method is characterized in that the overall process hasa carbon efficiency greater than 55%, greater than 60%, greater than62%, greater than 63%, greater than 64%, or greater than 65%. In certainembodiments, the method is characterized in that the overall process hasa carbon efficiency greater than 66%, greater than 67%, greater than68%, greater than 69%, or greater than 70%. In certain embodiments, themethod is characterized in that the overall process has a carbonefficiency between about 50% and about 60%. In certain embodiments, themethod is characterized in that the overall process has a carbonefficiency between about 55% and about 60%. In certain embodiments, themethod is characterized in that the overall process has a carbonefficiency between about 60% and about 64%. In certain embodiments, themethod is characterized in that the overall process has a carbonefficiency between about 64% and about 67%. In certain embodiments, themethod is characterized in that the overall process has a carbonefficiency between about 67% and about 70%.

In certain embodiments, step (b) of the method above comprises twosubsteps. In a first substep, the syngas stream from step (a) iscontacted with ethylene oxide to provide beta propiolactone along withan upgraded syngas stream having a higher H₂ to CO ratio than the syngasstream from step (a) and, in a second substep, the beta propiolactone isdirected to a second carbonylation reactor where it is contacted withthe upgraded syngas stream in the presence of a carbonylation catalyst(which may be the same as or different from the carbonylation catalystutilized in step the method comprises an additional step of convertingthe beta propiolactone to succinic anhydride. In certain embodimentssuch methods comprise an additional step of converting the succinicanhydride to a product selected from the group consisting of: succinicacid, 1,4 butanediol, tetrahydrofuran, gamma butyrolactone, or anycombination of two or more of these.

In certain embodiments where the method above comprises an additionalstep of converting beta propiolactone to succinic anhydride, theconversion is conducted in a second carbonylation reactor. In certainembodiments, the second carbonylation reactor is fed with the upgradedsyngas stream produced in step (b) where the upgraded syngas iscontacted with the beta propiolactone in the presence of a carbonylationcatalyst to further deplete the upgraded syngas stream of its CO therebyproviding a twice-upgraded syngas stream having a higher H₂ to CO ratiothan the upgraded syngas stream from step (c).

VII) Integrated Production of Methanol and EO Carbonylation Products

As described above, in certain embodiments, the present inventionencompasses methods for the integrated production of methanol fromsyngas derived from gasification.

In certain embodiments, such processes produce as final outputs, betapropiolactone or polypropiolactone (or derivatives of these such asacrylic acid, acrylate esters or superabsorbent polymers) by ethyleneoxide carbonylation and methanol or methanol-derived products suchdimethyl ether or olefins via a methanol-to-olefins process (MTO).

In certain embodiments, methods of the present invention comprise thesteps of:

-   -   a) Treating a carbon-based feedstock to provide a syngas stream        having a H₂ to CO ratio less than 2:1;    -   b) feeding this syngas stream to an epoxide carbonylation        reactor where the syngas stream is contacted with ethylene oxide        in the presence of a carbonylation catalyst to deplete the        syngas of at least a portion of its CO content and provide a        carbonylation product selected from the group consisting of:        beta propiolactone, polypropiolactone and succinic anhydride;    -   c) recovering an upgraded syngas stream from the carbonylation        reactor characterized in that the upgraded stream has a higher        H₂ to CO ratio than the syngas stream provided by step (a); and    -   d) feeding the upgraded syngas stream to a methanol synthesis        reactor.

In certain embodiments, step (a) of the method above comprises coalgasification. In certain embodiments, such methods are characterized inthat the syngas stream in step (a) has an H₂ to CO ratio of from about0.6:1 to about 0.8:1. In certain embodiments, such methods arecharacterized in that the syngas stream in step (a) has an H₂ to COratio of about 0.7:1.

In certain embodiments, step (a) of the method above comprises biomassgasification. In certain embodiments, the biomass is selected from thegroup consisting of: corn stover, sugar cane bagasse, switch grass,municipal solid waste, and wood waste. In certain embodiments, suchmethods are characterized in that the syngas stream in step (a) has anH₂ to CO ratio of from about 0.4:1 to about 0.8:1. In certainembodiments, such methods are characterized in that the syngas stream instep (a) has an H₂ to CO ratio of about 0.6:1. In certain embodiments,such methods are characterized in that the syngas stream in step (a) hasan H₂ to CO ratio of about 0.5:1.

In certain embodiments, the method above comprises an additional step ofcompressing the syngas stream prior to feeding it to the carbonylationreactor. In certain embodiments, the method above comprises anadditional step of removing sulfurous compounds from the syngas streamprior to feeding it to the carbonylation reactor. In certainembodiments, the method above comprises an additional step of drying thesyngas stream prior to feeding it to the carbonylation reactor. Incertain embodiments, the method above comprises an additional step ofremoving CO₂ from the syngas stream prior to feeding it to thecarbonylation reactor. In certain embodiments, the method above ischaracterized in that CO₂ is not removed from the syngas stream prior tofeeding it to the carbonylation reactor.

In certain embodiments, the product of step (b) of the method abovecomprises beta propiolactone and the method comprises an additional stepof converting the beta propiolactone to acrylic acid, or acrylateesters.

In certain embodiments, the product of step (b) of the method abovecomprises beta propiolactone and the method comprises an additional stepof converting the beta propiolactone to succinic anhydride. In certainembodiments such methods comprise an additional step of converting thesuccinic anhydride to a product selected from the group consisting of:succinic acid, 1,4 butanediol, tetrahydrofuran, gamma butyrolactone, orany combination of two or more of these.

In certain embodiments where the method above comprises an additionalstep of converting beta propiolactone to succinic anhydride, theconversion is conducted in a second carbonylation reactor. In certainembodiments, the second carbonylation reactor is also fed with thesyngas stream produced in step (a) where it is contacted with the betapropiolactone in the presence of a carbonylation catalyst to deplete thesyngas of at least a portion of its CO content and provide succinicanhydride as a second carbonylation product. In certain embodiments, asecond upgraded syngas stream, characterized in that it has a higher H₂to CO ratio that the syngas stream produced in step (a) is recoveredfrom the second carbonylation reactor. In certain embodiments, the firstand second upgraded syngas streams are combined and utilized in step(d).

In certain embodiments where the method above comprises an additionalstep of converting beta propiolactone to succinic anhydride, theconversion is conducted in a second carbonylation reactor which is fedwith the upgraded syngas stream produced in step (b) where it iscontacted with the beta propiolactone in the presence of a carbonylationcatalyst to further deplete the upgraded syngas stream of its CO therebyproviding a twice-upgraded syngas stream having a higher H₂ to CO ratiothan the upgraded syngas stream from step (c). In certain embodiments,the method comprises an additional step of recovering the twice upgradedsyngas stream from the second carbonylation reactor and feeding it tothe methanol reactor in step (d).

In certain embodiments, the product of step (b) of the method above ispolypropiolactone and the method comprises an additional step ofpyrolyzing the polypropiolactone to produce acrylic acid.

In certain embodiments, the carbonylation catalyst in step (b) of themethod above comprises a metal carbonyl compound. In certainembodiments, the metal carbonyl compound is selected from any of thosedescribed in Appendix I. In certain embodiments, the metal carbonylcompound comprises a cobalt carbonyl compound. In certain embodiments,metal carbonyl compound comprises a rhodium carbonyl compound. Incertain embodiments, the carbonylation catalyst in step (b) of themethod above comprises a metal carbonyl compound in combination withanother component selected from the group consisting of: organic bases,neutral Lewis acids, and cationic Lewis acids. In certain embodiments,the carbonylation catalyst in step (b) of the method above comprises ananionic cobalt carbonyl compound in combination with a cationic Lewisacid. In certain embodiments, such cationic Lewis acids comprise metalligand complexes. In certain embodiments, the metal ligand complexescomprise any complex described in Appendix II. In certain embodiments,such metal ligand complexes comprise a metal atom coordinated to amultidentate ligand. In certain embodiments, such metal ligand complexescomprise an aluminum or chromium atom. In certain embodiments, suchmetal ligand complexes comprise a porphyrin or salen ligand. In certainembodiments, the carbonylation catalyst in step (b) of the method abovecomprises any combination of a metal carbonyl compound from Appendix Iand a metal complex from Appendix II.

In certain embodiments, step (c) in the method above is characterized inthat the upgraded syngas stream recovered has an H₂ to CO ratio betweenabout 1.2:1 and about 3:1. In certain embodiments, the upgraded syngasstream recovered has an H₂ to CO ratio between about 1.6:1 and about2.8:1, between about 1.8:1 and about 2.6:1, between about 1.8:1 andabout 2.2:1, or between about 1.9:1 and about 2.1:1. In certainembodiments, the upgraded syngas stream recovered has an H₂ to CO ratioof about 2:1.

In certain embodiments, the method above is characterized in that thereaction pressure in the carbonylation reactor is higher than thereaction pressure in the methanol synthesis reactor. In certainembodiments, the upgraded syngas stream is fed to the methanol synthesisreactor without an intermediate compression step. In certainembodiments, the upgraded syngas stream exits the carbonylation reactorvia a backpressure regulator and is fed directly to the methanolsynthesis reactor.

In certain embodiments, the method above is characterized in that theupgraded syngas stream is treated to remove one or more components priorto use in the methanol synthesis step. In certain embodiments, theupgraded syngas stream is treated to remove residual solvent prior tofeeding the stream to the methanol synthesis reactor. In certainembodiments, the upgraded syngas stream is treated to remove residualepoxide prior to feeding the stream to the methanol synthesis reactor.In certain embodiments, the upgraded syngas stream is treated to removecarbon dioxide prior to feeding the stream to the methanol synthesisreactor.

In certain embodiments, the method above is characterized in that themethanol synthesis reactor in step (d) utilizes a catalyst comprisingone or more of, copper, alumina and zinc oxide.

In certain embodiments, the method above comprises an additional step offeeding methanol produced in the methanol reactor to an MTO reactorwhere it is converted to olefins. In certain embodiments, the MTOreactor converts the methanol to ethylene, propylene or a mixture ofethylene and propylene.

In embodiments where the process is integrated to an MTO reactor, thepossibility exists for a process that produces carbonylation productsderived entirely from the carbon source fed to the syngas productionstep. This is achieved by utilizing ethylene or propylene from the MTOstage to produce ethylene oxide or propylene oxide which is thenutilized as the feedstock for the carbonylation reactor.

Therefore, in certain embodiments, the present invention encompassesmethods for the production of 100% biomass-derived chemicals. In certainembodiments such chemicals are the result of the process depicted inFIG. 5. FIG. 5 shows an integrated process for production of acrylicacid from biomass. As shown, biomass is gasified in Gasifier 101 toproduce a syngas stream 101 having an H₂:CO ratio less than 1 (typically0.5-0.7:1). This is fed to Carbonylation Reactor 200 where it iscontacted with ethylene oxide in the presence of carbonylation catalyst.Carbonylation reactor produces beta propiolactone stream 209 along withupgraded syngas stream 210. Upgraded syngas stream 210 has an H2 to COratio around 2:1 and is therefore suitable for use in methanol synthesisreactor 600. The methanol from reactor 600 is fed to MTO reactor 700where it is converted to ethylene stream 212 (and optionally additionalstreams such as propylene and higher olefins, not shown). Ethylenestream 212 is directed to an oxidation reactor 800 where it is convertedto ethylene oxide. The resulting ethylene oxide is fed to carbonylationreactor 200 to react with syngas stream 101. To complete the acrylicacid synthesis the beta lactone stream 209 from the carbonylationreactor is fed to AA reactor 900 where it is converted to acrylic acid.The three carbon atoms in the resulting AA are all derived from thebiomass fed to reactor 101:

In one aspect, the present invention encompasses acrylic acid whereinall three carbon atoms are derived from biomass in an integratedgasification process characterized in that the carboxylic carbon atom isderived from CO in the syngas, and the two ethylene carbon atoms arederived from ethylene produced by MTO utilizing methanol formed from asyngas stream upgraded to increase its H2 content by carbonylation ofthe epoxide.

A closely related process provides biomass derived polymers such aspolypropiolactone (PPL) or poly(3-hydroxybutyrolactonc) (PHB). Suchprocesses either add a beta lactone polymerization reactor fed by thebeta lactone stream, or utilize conditions in the carbonylation reactorto produce polyester as the primary product. For the PHB process, theMTO reactor would be operated to provide a propylene stream which isthen oxidized to propylene oxide which is fed to the carbonylationreactor.

In certain other embodiments, the present invention encompasses methodsfor the production of 100% biomass-derived C4 chemicals. In certainembodiments such chemicals are the result of the process depicted inFIG. 6. FIG. 6 shows an integrated process for production of acrylicacid from biomass. As shown, biomass is gasified in Gasifier 101 toproduce a syngas stream 101 having an H₂:CO ratio less than 1 (typically0.5-0.7:1). This is fed to Carbonylation Reactor 200 where it iscontacted with ethylene oxide in the presence of carbonylation catalyst.Carbonylation reactor produces beta propiolactone stream 209 along withupgraded syngas stream 210. Upgraded syngas stream 210 has an H2 to COratio around 2:1 and is therefore suitable for use in methanol synthesisreactor 600. The methanol from reactor 600 is fed to MTO reactor 700where it is converted to ethylene stream 212 (and optionally additionalstreams such as propylene and higher olefins, not shown). Ethylenestream 212 is directed to an oxidation reactor 800 where it is convertedto ethylene oxide. The resulting ethylene oxide is fed to carbonylationreactor 200 to react with syngas stream 101. To complete the C4chemicals synthesis, the beta lactone stream 209 from the carbonylationreactor is fed to 2^(nd) carbonylation reactor 202 where it is convertedto succinic anhydride. Succinic anhydride stream 214 is fed tohydrogenation reactor where it is converted to C4 commodity chemicalssuch as 1,4 butanediol, tetrahydrofuran. GBL, or combinations of two ormore of these. The three carbon atoms in the resulting chemicals are allderived from the biomass fed to reactor 101:

In one aspect, the present invention encompasses C4 chemicals (THF, BDOand/or GBL) wherein all four carbon atoms are derived from biomass in anintegrated gasification process characterized in that the carbon atomsboned to oxygen atoms are derived from CO in syngas, and the two othercarbon atoms are derived from ethylene produced by MTO utilizingmethanol formed from a syngas stream upgraded to increase its H₂ contentby carbonylation of the epoxide.

In certain embodiments, the method above is characterized in that theoverall process has a carbon efficiency greater than 50%. That is, atleast 50% of the carbon atoms fed to the syngas production step arecontained in the combined products from the EO carbonylation reactor andthe methanol synthesis reactor. In certain embodiments, the method ischaracterized in that the overall process has a carbon efficiencygreater than 55%, greater than 60%, greater than 62%, greater than 63%,greater than 64%, or greater than 65%. In certain embodiments, themethod is characterized in that the overall process has a carbonefficiency greater than 66%, greater than 67%, greater than 68%, greaterthan 69%, or greater than 70%. In certain embodiments, the method ischaracterized in that the overall process has a carbon efficiencybetween about 50% and about 60%. In certain embodiments, the method ischaracterized in that the overall process has a carbon efficiencybetween about 55% and about 60%. In certain embodiments, the method ischaracterized in that the overall process has a carbon efficiencybetween about 60% and about 64%. In certain embodiments, the method ischaracterized in that the overall process has a carbon efficiencybetween about 64% and about 67%. In certain embodiments, the method ischaracterized in that the overall process has a carbon efficiencybetween about 67% and about 70%.

In certain embodiments, the method above is characterized in that themethanol synthesis process in step (d) is fed with syngas from thegasification process in step (a) without utilizing the water gas shiftreaction to increase its H₂ to CO ratio.

It is to be understood that the embodiments of the invention hereindescribed are merely illustrative of the application of the principlesof the invention. Reference herein to details of the illustratedembodiments is not intended to limit the scope of the claims, whichthemselves recite those features regarded as essential to the invention.

APPENDIX I Metal Carbonyl Compounds Suitable for Certain Methods of theInvention

In certain embodiments, a provided metal carbonyl compound comprises ananionic metal carbonyl moiety. In other embodiments, a provided metalcarbonyl compound comprises a neutral metal carbonyl compound. Incertain embodiments, a provided metal carbonyl compound comprises ametal carbonyl hydride or a hydrido metal carbonyl compound. In someembodiments, a provided metal carbonyl compound acts as a pre-catalystwhich reacts in situ with one or more reaction components to provide anactive species different from the compound initially provided. Suchpre-catalysts are specifically encompassed by the present invention asit is recognized that the active species in a given reaction may not beknown with certainty.

In certain embodiments, the metal carbonyl compound comprises an anionicmetal carbonyl species. In certain embodiments, such anionic metalcarbonyl species have the general formula [Q_(d)M′_(e)(CO)_(w)]^(y−),where Q is any ligand and need not be present, M′ is a metal atom, d isan integer between 0 and 8 inclusive, e is an integer between 1 and 6inclusive, w is a number such as to provide the stable anionic metalcarbonyl complex, and y is the charge of the anionic metal carbonylspecies. In certain embodiments, the anionic metal carbonyl has thegeneral formula [QM′(CO)_(w)]^(y−), where Q is any ligand and need notbe present, M′ is a metal atom, w is a number such as to provide thestable anionic metal carbonyl, and y is the charge of the anionic metalcarbonyl.

In certain embodiments, the anionic metal carbonyl species includemonoanionic carbonyl complexes of metals from groups 5, 7 or 9 of theperiodic table or dianionic carbonyl complexes of metals from groups 4or 8 of the periodic table. In some embodiments, the anionic metalcarbonyl compound contains cobalt or manganese. In some embodiments, theanionic metal carbonyl compound contains rhodium. Suitable anionic metalcarbonyl compounds include, but are not limited to: [Co(CO)₄]⁻,[Ti(CO)₆]²⁻ [V(CO)₆]⁻ [Rh(CO)₄]⁻, [Fe(CO)₄]²⁻ [Ru(CO)₄]²⁻, [Os(CO)₄]²⁻[Cr₂(CO)₁₀]²⁻ [Fe₂(CO)₈]²⁻ [Tc(CO)₅]⁻ [Re(CO)₅]⁻ and [Mn(CO)₅]⁻. Incertain embodiments, the anionic metal carbonyl comprises [Co(CO)₄]⁻. Insome embodiments, a mixture of two or more anionic metal carbonylcomplexes may be present in the polymerization system.

The term “such as to provide a stable anionic metal carbonyl” for[Q_(d)M′_(e)(CO)_(w)]^(y−) is used herein to mean that[Q_(d)M′_(e)(CO)_(w)]^(y−) is a species characterizable by analyticalmeans, e.g., NMR, IR, X-ray crystallography, Raman spectroscopy and/orelectron spin resonance (EPR) and isolable in catalyst form in thepresence of a suitable cation or a species formed in situ. It is to beunderstood that metals which can form stable metal carbonyl complexeshave known coordinative capacities and propensities to form polynuclearcomplexes which, together with the number and character of optionalligands Q that may be present and the charge on the complex willdetermine the number of sites available for CO to coordinate andtherefore the value of w. Typically, such compounds conform to the“18-electron rule”. Such knowledge is within the grasp of one havingordinary skill in the arts pertaining to the synthesis andcharacterization of metal carbonyl compounds.

In embodiments where the provided metal carbonyl compound is an anionicspecies, one or more cations must also necessarily be present. Thepresent invention places no particular constraints on the identity ofsuch cations. For example, in certain embodiments, the metal carbonylanion is associated with a cationic Lewis acid. In other embodiments acation associated with a provided anionic metal carbonyl compound is asimple metal cation such as those from Groups 1 or 2 of the periodictable (e.g. Na⁺, Li⁺, K⁺, Mg²⁺ and the like). In other embodiments acation associated with a provided anionic metal carbonyl compound is abulky non electrophilic cation such as an ‘onium salt’ (e.g. Bu₄N⁺,PPN⁺, Ph₄P⁺ Ph₄As⁺, and the like.

In certain embodiments, a provided metal carbonyl compound comprises aneutral metal carbonyl. In certain embodiments, such neutral metalcarbonyl compounds have the general formula Q_(d)M′_(e)(CO)_(w′), whereQ is any ligand and need not be present, M′ is a metal atom, d is aninteger between 0 and 8 inclusive, e is an integer between 1 and 6inclusive, and w′ is a number such as to provide the stable neutralmetal carbonyl complex. In certain embodiments, the neutral metalcarbonyl has the general formula QM′(CO)_(w′). In certain embodiments,the neutral metal carbonyl has the general formula M′(CO)_(w′). Incertain embodiments, the neutral metal carbonyl has the general formulaQM′₂(CO)_(w′). In certain embodiments, the neutral metal carbonyl hasthe general formula M′₂(CO)_(w′). Suitable neutral metal carbonylcompounds include, but are not limited to: Ti(CO)₇; V₂(CO)₁₂; Cr(CO)₆;Mo(CO)₆; W(CO)₆Mn₂(CO)₁₀, Te₂(CO)₁₀, and Re₂(CO)₁₀ Fe(CO)₅, Ru(CO)₅ andOs(CO)₅ Ru₃(CO)₁₂, and Os₃(CO)₁₂ Fe₃(CO)₁₂ and Fe₂(CO)₉ Co₄(CO)₁₂,Rh₄(CO)₁₂, Rh₆(CO)₁₆, and Ir₄(CO)₁₂, Co₂(CO)₈ Ni(CO)₄.

The term “such as to provide a stable neutral metal carbonyl forQ_(d)M′_(e)(CO)_(w′) is used herein to mean that Q_(d)M′_(e)(CO)_(w′) isa species characterizable by analytical means, e.g., NMR, IR, X-raycrystallography, Raman spectroscopy and/or electron spin resonance (EPR)and isolable in pure form or a species formed in situ. It is to beunderstood that metals which can form stable metal carbonyl complexeshave known coordinative capacities and propensities to form polynuclearcomplexes which, together with the number and character of optionalligands Q that may be present will determine the number of sitesavailable for CO to coordinate and therefore the value of w′. Typically,such compounds conform to stoichiometries conforming to the “18-electronrule”. Such knowledge is within the grasp of one having ordinary skillin the arts pertaining to the synthesis and characterization of metalcarbonyl compounds.

In certain embodiments, one or more of the CO ligands of any of themetal carbonyl compounds described above is replaced with a ligand Q. Incertain embodiments, Q is a phosphine ligand. In certain embodiments, Qis a triaryl phosphine. In certain embodiments, Q is trialkyl phosphine.In certain embodiments, Q is a phosphite ligand. In certain embodiments,Q is an optionally substituted cyclopentadienyl ligand. In certainembodiments, Q is cp. In certain embodiments, Q is cp*.

In certain embodiments, polymerization systems of the present inventioncomprise hydrido metal carbonyl compounds. In certain embodiments, suchcompounds are provided as the hydrido metal carbonyl compound, while inother embodiments, the hydrido metal carbonyl is generated in situ byreaction with hydrogen gas, or with a protic acid using methods known inthe art (see for example Chem. Rev., 1972, 72 (3), pp 231-281 DOI:10.1021/cr60277a003, the entirety of which is incorporated herein byreference).

In certain embodiments, the hydrido metal carbonyl (either as providedor generated in situ) comprises one or more of HCo(CO)₄, HCoQ(CO)₃,HMn(CO)₅, HMn(CO)₄Q, HW(CO)₃Q, HRe(CO)₅, HMo(CO)₃Q, HOs(CO)₂Q,HMo(CO)₂Q₂, HFe(CO₂)Q, HW(CO)₂Q₂, HRuCOQ₂, H₂Fe(CO)₄ or H₂Ru(CO)₄, whereeach Q is independently as defined above and in the classes andsubclasses herein. In certain embodiments, the metal carbonyl hydride(either as provided or generated in situ) comprises HCo(CO)₄. In certainembodiments, the metal carbonyl hydride (either as provided or generatedin situ) comprises HCo(CO)₃PR₃, where each R is independently anoptionally substituted aryl group, an optionally substituted C₁₋₂₀aliphatic group, an optionally substituted C₁₋₁₀ alkoxy group, or anoptionally substituted phenoxy group. In certain embodiments, the metalcarbonyl hydride (either as provided or generated in situ) comprisesHCo(CO)₃cp, where cp represents an optionally substituted pentadienylligand. In certain embodiments, the metal carbonyl hydride (either asprovided or generated in situ) comprises HMn(CO)₅. In certainembodiments, the metal carbonyl hydride (either as provided or generatedin situ) comprises H₂Fe(CO)₄.

In certain embodiments, for any of the metal carbonyl compoundsdescribed above, M′ comprises a transition metal. In certainembodiments, for any of the metal carbonyl compounds described above, M′is selected from Groups 5 (Ti) to 10 (Ni) of the periodic table. Incertain embodiments, M′ is a Group 9 metal. In certain embodiments, M′is Co. In certain embodiments. M′ is Rh. In certain embodiments, M′ isIr. In certain embodiments, M′ is Fe. In certain embodiments, M′ is Mn.

APPENDIX II Lewis Acidic Metal Complexes Suitable for Certain Methods ofthe Invention

In certain embodiments where a carbonylation catalyst utilized in any ofthe methods above comprises a metal carbonyl compound in combinationwith a cationic Lewis acid, the Lewis acid has a formula[(L^(e))_(v)M_(b)]^(z+), where:

L^(e) is a ligand where, when two or more L^(e) are present, each may bethe same or different;

M is a metal atom where, when two M are present, each may be the same ordifferent;

v is an integer from 1 to 4 inclusive;

b is an integer from 1 to 2 inclusive; and

z is an integer greater than 0 that represents the cationic charge onthe metal complex.

In certain embodiments, provided Lewis acids conform to structure I:

wherein:

is a multidentate ligand;

M is a metal atom coordinated to the multidentate ligand;

a is the charge of the metal atom and ranges from 0 to 2; and

In certain embodiments, provided metal complexes conform to structureII:

Where a is as defined above (each a may be the same or different), and

M¹ is a first metal atom;

M² is a second metal atom;

comprises a multidentate ligand system capable of coordinating bothmetal atoms.

For sake of clarity, and to avoid confusion between the net and totalcharge of the metal atoms in complexes I and II and other structuresherein, the charge (a⁺) shown on the metal atom in complexes I and IIabove represents the net charge on the metal atom after it has satisfiedany anionic sites of the multidentate ligand. For example, if a metalatom in a complex of formula I were Cr(III), and the ligand wereporphyrin (a tetradentate ligand with a charge of −2), then the chromiumatom would have a net charge of +1, and a would be 1.

Suitable multidentate ligands include, but are not limited to: porphyrinderivatives 1, salen derivatives 2,dibenzotetramethyltetraaza[14]annulene (tmtaa) derivatives 3,phthalocyaninate derivatives 4, derivatives of the Trost ligand 5,tetraphenylporphyrin derivatives 6, and corrole derivatives 7. Incertain embodiments, the multidentate ligand is a salen derivative. Inother embodiments, the multidentate ligand is a porphyrin derivative. Inother embodiments, the multidentate ligand is a tetraphenylporphyrinderivative. In other embodiments, the multidentate ligand is a corrolederivative.

where each of R^(c), R^(d), R^(a), R^(1a), R^(2a), R^(3a), R^(1a′),R^(2a′), R^(3a′), and M, is as defined and described in the classes andsubclasses herein.

In certain embodiments, Lewis acids provided in polymerization systemsof the present invention comprise metal-porphinato complexes. In certainembodiments, the moiety

has the structure:

-   -   where each of M and a is as defined above and described in the        classes and subclasses herein, and    -   R^(d) at each occurrence is independently hydrogen, halogen,        —OR⁴, —NR^(y) ₂, —SR, —CN, —NO₂, —SO₂R^(y), —SOR^(y), —SO₂NR^(y)        ₂: —CNO, —NRSO₂R^(y), —NCO, —N₃, —SiR₃; or an optionally        substituted group selected from the group consisting of C₁₋₂₀        aliphatic; C₁₋₂₀ heteroaliphatic having 1-4 heteroatoms        independently selected from the group consisting of nitrogen,        oxygen, and sulfur; 6- to 10-membered aryl; 5- to 10-membered        heteroaryl having 1-4 heteroatoms independently selected from        nitrogen, oxygen, and sulfur; and 4- to 7-membered heterocyclic        having 1-2 heteroatoms independently selected from the group        consisting of nitrogen, oxygen, and sulfur, where two or more        R^(d) groups may be taken together to form one or more        optionally substituted rings, where each R^(y) is independently        hydrogen, an optionally substituted group selected the group        consisting of acyl; carbamoyl, arylalkyl; 6- to 10-membered        aryl; C₁₋₁₂ aliphatic; C₁₋₁₂ heteroaliphatic having 1-2        heteroatoms independently selected from the group consisting of        nitrogen, oxygen, and sulfur; 5- to 10-membered heteroaryl        having 1-4 heteroatoms independently selected from the group        consisting of nitrogen, oxygen, and sulfur; 4- to 7-membered        heterocyclic having 1-2 heteroatoms independently selected from        the group consisting of nitrogen, oxygen, and sulfur; an oxygen        protecting group; and a nitrogen protecting group; two R^(y) on        the same nitrogen atom are taken with the nitrogen atom to form        an optionally substituted 4- to 7-membered heterocyclic ring        having 0-2 additional heteroatoms independently selected from        the group consisting of nitrogen, oxygen, and sulfur; and each        R⁴ independently is a hydroxyl protecting group or R^(y).

In certain embodiments, the moiety

has the structure:

where M, a and R^(d) are as defined above and in the classes andsubclasses herein.

In certain embodiments, the moiety

as the structure:

where M, a and R^(d) are as defined above and in the classes andsubclasses herein.

In certain embodiments, Lewis acids included in polymerization systemsof the present invention comprise metallo salenate complexes. In certainembodiments, the moiety

has the structure:

wherein:

-   -   M, and a are as defined above and in the classes and subclasses        herein.    -   R^(1a), R^(1a′), R^(2a), R^(2a′), R^(3a), and R^(3a′) are        independently hydrogen, halogen, —OR⁴, —NR^(y) ₂, —SR, —CN,        —NO₂, —SO₂R^(y), —SOR, —SO₂NR^(y) ₂; —CNO, —NRSO₂R^(y), —NCO,        —N₃, —SiR₃; or an optionally substituted group selected from the        group consisting of C₁₋₂₀ aliphatic; C₁₋₂₀ heteroaliphatic        having 1-4 heteroatoms independently selected from the group        consisting of nitrogen, oxygen, and sulfur; 6- to 10-membered        aryl; 5- to 10-membered heteroaryl having 1-4 heteroatoms        independently selected from nitrogen, oxygen, and sulfur; and 4-        to 7-membered heterocyclic having 1-2 heteroatoms independently        selected from the group consisting of nitrogen, oxygen, and        sulfur; wherein each R, R⁴, and R^(y) is independently as        defined above and described in classes and subclasses herein,    -   wherein any of (R^(2a′) and R^(3a′)), (R^(2a) and R^(3a)),        (R^(1a) and R^(2a)), and (R^(1a′) and R^(2a′)) may optionally be        taken together with the carbon atoms to which they are attached        to form one or more rings which may in turn be substituted with        one or more R groups; and    -   R^(4a) is selected from the group consisting of:

where

-   -   R^(c) at each occurrence is independently hydrogen, halogen,        —OR, —NR^(y) ₂, —SR^(y), —CN, —NO₂, —SO₂R^(y), —SOR^(y),        —SO₂NR^(y) ₂; —CNO, —NRSO₂R^(y), —NCO, —N₃, —SiR₃; or an        optionally substituted group selected from the group consisting        of C₁₋₂₀ aliphatic; C₁₋₂₀ heteroaliphatic having 1-4 heteroatoms        independently selected from the group consisting of nitrogen,        oxygen, and sulfur; 6- to 10-membered aryl; 5- to 10-membered        heteroaryl having 1-4 heteroatoms independently selected from        nitrogen, oxygen, and sulfur, and 4- to 7-membered heterocyclic        having 1-2 heteroatoms independently selected from the group        consisting of nitrogen, oxygen, and sulfur;    -   where:        -   two or more R^(c) groups may be taken together with the            carbon atoms to which they are attached and any intervening            atoms to form one or more rings;        -   when two R^(c) groups are attached to the same carbon atom,            they may be taken together along with the carbon atom to            which they are attached to form a moiety selected from the            group consisting of: a 3- to 8-membered spirocyclic ring, a            carbonyl, an oxime, a hydrazone, an imine; and an optionally            substituted alkene;    -   Y is a divalent linker selected from the group consisting of:        —NR^(y)—, —N(R)C(O)—, —C(O)NR^(y)—, —O—, —C(O)—, —OC(O)—,        —C(O)O—, —S—, —SO—, —SO₂—, —C(═S)—, —C(═NR^(y))—, —N═N—; a        polyether; a C₃ to C₈ substituted or unsubstituted carbocycle;        and a C₁ to C₈ substituted or unsubstituted heterocycle;    -   m′ is 0 or an integer from 1 to 4, inclusive;    -   q is 0 or an integer from 1 to 4, inclusive; and    -   x is 0, 1, or 2.

In certain embodiments, a provided Lewis acid comprises a metallo salencompound, as shown in formula Ia:

-   -   wherein each of M, R^(d), and a, is as defined above and in the        classes and subclasses herein,

represents is an optionally substituted moiety linking the two nitrogenatoms of the diamine portion of the salen ligand, where

is selected from the group consisting of a C₃-C₁₄ carbocycle, a C₆-C₁₀aryl group, a C₃-C₁₄ heterocycle, and a C₅-C₁₀ heteroaryl group; or anoptionally substituted C₂₋₂₀ aliphatic group, wherein one or moremethylene units are optionally and independently replaced by —NR^(y)—,—N(R^(y))C(O)—, —C(O)N(R^(y))—, —OC(O)N(R^(y))—, —N(R^(y))C(O)O—,—OC(O)O—, —O—, —C(O)—, —OC(O)—, —C(O)O—, —S—, —SO—, —SO₂—, —C(═S)—,—C(═NR^(y))—, —C(═NOR^(y))— or —N═N—.

In certain embodiments metal complexes having formula Ia above, at leastone of the phenyl rings comprising the salicylaldehyde-derived portionof the metal complex is independently selected from the group consistingof:

In certain embodiments, a provided Lewis acid comprises a metallo salencompound, conforming to one of formulae Va or Vb:

-   -   where M, a, R^(d), R^(1a), R^(3a), R^(1a′), R^(3a′), and

are as defined above and in the classes and subclasses herein.

In certain embodiments of metal complexes having formulae Va or Vb, eachR^(1′) and R^(3′) is, independently, optionally substituted C₁-C₂₀aliphatic.

In certain embodiments, the moiety

comprises an optionally substituted 1,2-phenyl moiety.

In certain embodiments, Lewis acids included in polymerization systemsof the present invention comprise metal-tmtaa complexes. In certainembodiments, the moiety

has the structure:

-   where M, a and R^(d) are as defined above and in the classes and    subclasses herein, and-   R^(e) at each occurrence is independently hydrogen, halogen, —OR,    —NR₂, —SR, —CN, —NO₂, —SO₂R, —SOR, —SO₂NR₂; —CNO, —NRSO₂R, —NCO,    —N₃, —SiR₃; or al optionally substituted group selected from the    group consisting of C₁₋₂₀ aliphatic; C₁₋₂₀ heteroaliphatic having    1-4 heteroatoms independently selected from the group consisting of    nitrogen, oxygen, and sulfur; 6- to 10-membered aryl; 5- to    10-membered heteroaryl having 1-4 heteroatoms independently selected    from nitrogen, oxygen, and sulfur; and 4- to 7-membered heterocyclic    having 1-2 heteroatoms independently selected from the group    consisting of nitrogen, oxygen, and sulfur.

In certain embodiments, the moiety

has the structure:

-   -   where each of M, a, R^(c) and R^(d) is as defined above and in        the classes and subclasses herein.

In certain embodiments, where polymerization systems of the presentinvention include a Lewis acidic metal complex, the metal atom isselected from the periodic table groups 2-13, inclusive. In certainembodiments, M is a transition metal selected from the periodic tablegroups 4, 6, 11, 12 and 13. In certain embodiments, M is aluminum,chromium, titanium, indium, gallium, zinc cobalt, or copper. In certainembodiments, M is aluminum. In other embodiments, M is chromium.

In certain embodiments. M has an oxidation state of +2. In certainembodiments, M is Zn(II), Cu(II), Mn(II), Co(II), Ru(II), Fe(II),Co(II), Rh(II), Ni(II), Pd(II) or Mg(II). In certain embodiments M isZn(II). In certain embodiments M is Cu(II).

In certain embodiments. M has an oxidation state of +3. In certainembodiments, M is Al(III), Cr(III), Fe(III), Co(III), Ti(III) In(III),Ga(III) or Mn(III). In certain embodiments M is Al(III). In certainembodiments M is Cr(III).

In certain embodiments, M has an oxidation state of +4. In certainembodiments, M is Ti(IV) or Cr(IV).

In certain embodiments, M¹ and M² are each independently a metal atomselected from the periodic table groups 2-13, inclusive. In certainembodiments, M is a transition metal selected from the periodic tablegroups 4, 6, 11, 12 and 13. In certain embodiments, M is aluminum,chromium, titanium, indium, gallium, zinc cobalt, or copper. In certainembodiments, M is aluminum. In other embodiments, M is chromium. Incertain embodiments, M¹ and M² are the same. In certain embodiments, M¹and M² are the same metal, but have different oxidation states. Incertain embodiments, M¹ and M² are different metals.

In certain embodiments, one or more of M¹ and M² has an oxidation stateof +2. In certain embodiments, M¹ is Zn(II), Cu(II), Mn(II), Co(II),Ru(II), Fe(II), Co(II), Rh(II), Ni(II), Pd(II) or Mg(II). In certainembodiments M¹ is Zn(II). In certain embodiments M¹ is Cu(II). Incertain embodiments, M² is Zn(II), Cu(II), Mn(II), Co(II), Ru(II),Fe(II), Co(II), Rh(II), Ni(II), Pd(II) or Mg(II). In certain embodimentsM² is Zn(II). In certain embodiments M² is Cu(II).

In certain embodiments, one or more of M¹ and M² has an oxidation stateof +3. In certain embodiments, M¹ is Al(III), Cr(III), Fe(III), Co(III),Ti(III) In(III), Ga(III) or Mn(III). In certain embodiments M¹ isAl(III). In certain embodiments M¹ is Cr(III). In certain embodiments,M² is Al(III), Cr(III), Fe(III), Co(III), Ti(III) In(III), Ga(III) orMn(III). In certain embodiments M² is Al(III). In certain embodiments M²is Cr(III).

In certain embodiments, one or more of M¹ and M² has an oxidation stateof +4. In certain embodiments, M¹ is Ti(TV) or Cr(IV). In certainembodiments, M² is Ti(TV) or Cr(IV).

In certain embodiments, one or more neutral two electron donorscoordinate to M M¹ or M² and fill the coordination valence of the metalatom. In certain embodiments, the neutral two electron donor is asolvent molecule. In certain embodiments, the neutral two electron donoris an ether. In certain embodiments, the neutral two electron donor istetrahydrofuran, diethyl ether, acetonitrile, carbon disulfide, orpyridine. In certain embodiments, the neutral two electron donor istetrahydrofiran. In certain embodiments, the neutral two electron donoris an epoxide. In certain embodiments, the neutral two electron donor isan ester or a lactone.

What is claimed is:
 1. A method for the integrated production ofchemicals comprising the steps of: a) in a first reaction zone,contacting an epoxide in the presence of a carbonylation catalyst with asyngas stream containing hydrogen and carbon monoxide thereby causingcarbon monoxide in the industrial gas stream to react with the epoxideto provide an epoxide carbonylation product, b) removing an upgraded gasstream from the first reaction zone wherein the upgraded gas stream hasa higher hydrogen to carbon monoxide than the starting syngas stream,and c) in a second reaction zone, utilizing the upgraded gas stream toconduct a second chemical process requiring a hydrogen to CO ratiohigher than the ratio in the industrial gas stream utilized in step (a).2. The method of claim 1, wherein the syngas stream has a molar hydrogento CO ratio between 0.5:1 and 1.2:1, and the upgraded gas stream has ahydrogen to CO ratio of at least 1.9:1.
 3. The method of claim 1,wherein the second chemical process comprises Fischer Tropsch synthesis.4. The method of claim 1, wherein the second chemical process comprisesreaction on a fuel cell.
 5. The method of claim 1, wherein the secondchemical process comprises hydrogenation.
 6. The method of claim 1,wherein the epoxide carbonylation product is selected from the groupconsisting of: optionally substituted beta lactone, optionallysubstituted succinic anhydride, and a polyester resulting fromalternating polymerization of CO and the epoxide.
 7. The method of claim1, wherein the epoxide is ethylene oxide.
 8. The method of claim 7,wherein the carbonylation product is beta propiolactone.
 9. The methodof claim 7, wherein the epoxide carbonylation product is succinicanhydride, and the upgraded gas stream has a molar hydrogen to CO ratiogreater than 5.1.
 10. The method of claim 9, wherein and the upgradedgas stream has a hydrogen to CO ratio greater than 10:1, greater than20:1, greater than 50:1, greater than 100:1, or greater than 1,000:1.11. The method of claim 9, wherein the upgraded gas stream issubstantially free of carbon monoxide.